WorldWideScience

Sample records for acidic sulfate aerosols

  1. The Pacific Marine aerosol: Evidence for natural acid sulfates

    Science.gov (United States)

    Clarke, Antony D.; Ahlquist, Norman C.; Covert, David S.

    1987-04-01

    Optical, chemical, and physical measurements of marine boundary layer aerosol were made during two oceanographic cruises in the central Pacific in the fall of 1983 and spring of 1984. Both cruises revealed a ubiquitous accumulation mode atmospheric aerosol that showed marked increases in the region of equatorial upwelling, 4°N to 15°S, between Hawaii and Tahiti. Changes in the aerosol size distribution in response to thermal conditioning revealed properties consistent with those of sulfuric acid and/or ammonium sulfate/bisulfate depending upon the sampling location. Changes in the apparent acidity of the accumulation mode varied in conjunction with physical and chemical properties of the region sampled, while the number concentration suggests that it is the dominant and possibly limiting aerosol for cloud condensation nuclei in the remote central Pacific.

  2. Sulfuric acid deposition from stratospheric geoengineering with sulfate aerosols

    KAUST Repository

    Kravitz, Ben

    2009-07-28

    We used a general circulation model of Earth\\'s climate to conduct geoengineering experiments involving stratospheric injection of sulfur dioxide and analyzed the resulting deposition of sulfate. When sulfur dioxide is injected into the tropical or Arctic stratosphere, the main additional surface deposition of sulfate occurs in midlatitude bands, because of strong cross-tropopause flux in the jet stream regions. We used critical load studies to determine the effects of this increase in sulfate deposition on terrestrial ecosystems by assuming the upper limit of hydration of all sulfate aerosols into sulfuric acid. For annual injection of 5 Tg of SO2 into the tropical stratosphere or 3 Tg of SO2 into the Arctic stratosphere, neither the maximum point value of sulfate deposition of approximately 1.5 mEq m−2 a−1 nor the largest additional deposition that would result from geoengineering of approximately 0.05 mEq m−2 a−1 is enough to negatively impact most ecosystems.

  3. Sulfuric acid-ammonium sulfate aerosol: optical detection in the St. Louis region.

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    Charlson, R J; Vanderpol, A H; Covert, D S; Waggnoner, A P; Ahlquist, N C

    1974-04-12

    Nephelometric sensing of the deliquescence of ammonium sulfate produced by the reaction of sulfuric acid or ammonium bisulfate aerosol with ammonia provides a means for detecting these substances in air. Field experiments show them to be the dominant substances in the submicrometer, light-scattering aerosol in the St. Louis region.

  4. The partitioning of Nitric Acid between the gas phase and condensed phase of aqueous sulfate aerosols.

    Science.gov (United States)

    Mentel, T. F.; Folkers, M.; Sebald, H.; Wahner, A.

    2001-12-01

    The heterogeneous hydrolysis of N2O_5 on aqueous aerosol surfaces is an important source of atmospheric HNO3. We generated HNO3 by heterogeneous hydrolysis of N2O_5 on aqueous ammonium and sodium sulfate aerosols and studied its partitioning between the gas phase and the aerosol phase. The experiments were performed in the large aerosol chamber at the FZ-Jülich at several relative humidities. Gas phase processes and the composition of the aerosols were monitored on-line simultaneously by FTIR spectroscopy and by Steam Jet Aerosol Collection/Ion Chromatography. The aerosol size distributions in the range of 20 nm to 5 μ m were measured by differential electromobility classification and by aerodynamic particle sizing. In the presence of aqueous bisulfate and sulfate aerosols a fast heterogeneous formation HNO3 is observed. (The reaction probability of N2O_5 is about 0.02.) In the case of the acidic bisulfate aerosols the major fraction of heterogeneously formed HNO3 resides in the gas phase. For neutral sulfate aerosols a significant fraction of HNO3 is taken up by the condensed phase of the aerosols. This leads to a distinctive growth of the aerosol population during the heterogeneous hydrolysis of N2O_5, which is observable in the number size distribution as well as in IR extinction measurements. The observed partitioning of HNO3 between gas phase and aqueous aerosol phase can be quantitatively understood by a Pitzer based thermodynamic model for salt solutions of high ionic strength. The model calculations and low resolution FTIR spectroscopy demonstrate that protonation of sulfate to bisulfate is the driving force for the uptake of HNO3 in neutral sulfate aerosols.

  5. High aerosol acidity despite declining atmospheric sulfate concentrations over the past 15 years

    Science.gov (United States)

    Weber, Rodney J.; Guo, Hongyu; Russell, Armistead G.; Nenes, Athanasios

    2016-04-01

    Particle acidity affects aerosol concentrations, chemical composition and toxicity. Sulfate is often the main acid component of aerosols, and largely determines the acidity of fine particles under 2.5 μm in diameter, PM2.5. Over the past 15 years, atmospheric sulfate concentrations in the southeastern United States have decreased by 70%, whereas ammonia concentrations have been steady. Similar trends are occurring in many regions globally. Aerosol ammonium nitrate concentrations were assumed to increase to compensate for decreasing sulfate, which would result from increasing neutrality. Here we use observed gas and aerosol composition, humidity, and temperature data collected at a rural southeastern US site in June and July 2013 (ref. ), and a thermodynamic model that predicts pH and the gas-particle equilibrium concentrations of inorganic species from the observations to show that PM2.5 at the site is acidic. pH buffering by partitioning of ammonia between the gas and particle phases produced a relatively constant particle pH of 0-2 throughout the 15 years of decreasing atmospheric sulfate concentrations, and little change in particle ammonium nitrate concentrations. We conclude that the reductions in aerosol acidity widely anticipated from sulfur reductions, and expected acidity-related health and climate benefits, are unlikely to occur until atmospheric sulfate concentrations reach near pre-anthropogenic levels.

  6. TOTAL PARTICLE, SULFATE, AND ACIDIC AEROSOL EMISSIONS FROM KEROSENE SPACE HEATERS

    Science.gov (United States)

    Chamber studies were conducted on four unvented kerosene space heaters to assess emissions of total particle, sulfate, and acidic aerosol. The heaters tested represented four burner designs currently in use by the public. Kerosene space heaters are a potential source of fine part...

  7. Airway responses to sulfate and sulfuric acid aerosols in asthmatics. An exposure-response relationship.

    Science.gov (United States)

    Utell, M J; Morrow, P E; Speers, D M; Darling, J; Hyde, R W

    1983-09-01

    Epidemiologic studies support an association between elevated levels of sulfates and increased symptoms in asthmatics. To determine if these pollutants produce airway responses, 17 asthmatics inhaled the following sulfates: sodium bisulfate, ammonium sulfate, ammonium bisulfate (NH4HSO4), or sulfuric acid (H2SO4) aerosols with an aerodynamic diameter of 0.80 micron at concentrations of 100 micrograms/m3, 450 micrograms/m3, and 1,000 micrograms/m3. A sodium chloride (NaCl) aerosol of similar characteristics, administered by double-blind randomization, served as a control. Subjects breathed these aerosols for a 16-minute period via a mouthpiece. Deposition studies showed 54 to 65% retention of the inhaled aerosols. At the 1,000 micrograms/m3 concentration, the Threshold Limit Value for occupational exposure, H2SO4 and NH4HSO4 inhalation produced significant reductions in specific airway conductance (SGaw) (p less than 0.05) and forced expiratory volume in one second (p less than 0.01) compared with NaCl or pre-exposure values. At the 450 micrograms/m3 concentration, only H2SO4 inhalation produced a significant reduction in SGaw (p less than 0.01). At 100 micrograms/m3, a level 3 to 5 times greater than peak urban levels, no significant change in airway function occurred after any sulfate exposure. These data indicate that asthmatics demonstrate bronchoconstriction after brief exposure to common acidic sulfate pollutants.

  8. Ice Formation by Sulfate and Sulfuric Acid Aerosol Particles under Upper-Tropospheric Conditions.

    Science.gov (United States)

    Chen, Yalei; Demott, Paul J.; Kreidenweis, Sonia M.; Rogers, David C.; Eli Sherman, D.

    2000-11-01

    Ice formation in ammoniated sulfate and sulfuric acid aerosol particles under upper-tropospheric conditions was studied using a continuous flow thermal diffusion chamber. This technique allowed for particle exposure to controlled temperatures and relative humidities for known residence times. The phase states of (NH4)2SO4 and NH4HSO4 particles were found to have important impacts on their ice formation capabilities. Dry (NH4)2SO4 particles nucleated ice only at high relative humidity (RH 94%) with respect to water at temperatures between 40° and 60°C. This result suggested either an impedance or finite time dependence to deliquescence and subsequent homogeneous freezing nucleation. Ammonium sulfate particles that entered the diffusion chamber in a liquid state froze homogeneously at relative humidities that were 10% lower than where ice nucleated on initially dry particles. Likewise, crystalline or partially crystallized (as letovicite) NH4HSO4 particles required higher relative humidities for ice nucleation than did initially liquid bisulfate particles. Liquid particles of size 0.2 m composed of either ammonium sulfate or bisulfate froze at lower relative humidity at upper-tropospheric temperatures than did 0.05-m sulfuric acid aerosol particles. Comparison of calculated homogeneous freezing point depressions suggest that size effects on freezing may be more important than the degree of ammoniation of the sulfate compound.

  9. A study of the phase transition behavior of internally mixed ammonium sulfate - malonic acid aerosols

    Directory of Open Access Journals (Sweden)

    C. F. Braban

    2004-01-01

    Full Text Available This is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS - malonic acid (MA - water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25fMAfMA=0.9, the crystallization relative humidity of MA was lowered from RH=6% to less than 1%. Similarly, at fMA=0.4, the AS component did not crystallize. The atmospheric implications of the results are discussed.

  10. A study of the phase transition behavior of mixed ammonium sulfate – malonic acid aerosols

    Directory of Open Access Journals (Sweden)

    C. F. Braban

    2004-06-01

    Full Text Available This is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS – malonic acid (MA – water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25<fMA<0.90, no distinct "deliquescence" was observed, contrary to the observed behavior in the binary systems. The crystallization of both the MA and AS components is suppressed by the presence of the other component in the aerosol. At fMA=0.9, the crystallization relative humidity of MA was lowered from RH=6% to less than 1%. Similarly, at fMA=0.4, the AS component did not crystallize. The atmospheric implications of the results are discussed.

  11. Comparative biological potency of acidic sulfate aerosols: implications for the interpretation of laboratory and field studies.

    Science.gov (United States)

    Schlesinger, R B; Chen, L C

    1994-04-01

    Biological responses to inhaled acid sulfates result from the deposition of hydrogen ion (H+) on airway surfaces. Thus, effects from sulfuric acid and ammonium bisulfate, the two major ambient species, have been assumed to be the same for a given H+ concentration within the exposure atmosphere, assuming similar respiratory tract deposition patterns. However, recent inhalation studies have indicated that sulfuric acid is disproportionately potent compared to ammonium bisulfate when the H+ content of the exposure atmosphere is considered, suggesting that some factors following inhalation affect the amount of H+ contacting airway surfaces. This study assessed a mechanism potentially underlying this phenomenon, namely, the extent of neutralization by respiratory tract ammonia. This was evaluated using a physical model system designed to mimic transit of these aerosols in the upper respiratory tract of the animal model used in this laboratory, the rabbit. The results suggest that for equal exposure quantities of H+, more acid would be deposited when sulfuric acid is inhaled than when ammonium bisulfate is inhaled. Furthermore, results from a series of in vitro exposures of tracheal epithelial cells to sulfuric acid and ammonium bisulfate aerosols indicated that the biological response is a function of the total mass (ionic) concentration of H+ deliverable to the cells or the total extractable H+ per particle. The results of this study have possible implications for ambient monitoring of particulate-associated strong acidity, suggesting that it may be necessary to specilate such measures into the relative amounts of H+ as sulfuric acid or ammonium bisulfate in order to most accurately relate atmospheric acid levels to observed health effects. In addition, since much of the ambient particulate-associated H+ exists as sulfuric acid/ammonium bisulfate mixtures rather than pure compounds, H(+)-associated health effects from controlled exposure studies of sulfuric acid may

  12. Isotopic constraints on the role of hypohalous acids in sulfate aerosol formation in the remote marine boundary layer

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    Chen, Qianjie; Geng, Lei; Schmidt, Johan A.; Xie, Zhouqing; Kang, Hui; Dachs, Jordi; Cole-Dai, Jihong; Schauer, Andrew J.; Camp, Madeline G.; Alexander, Becky

    2016-09-01

    Sulfate is an important component of global atmospheric aerosol, and has partially compensated for greenhouse gas-induced warming during the industrial period. The magnitude of direct and indirect radiative forcing of aerosols since preindustrial times is a large uncertainty in climate models, which has been attributed largely to uncertainties in the preindustrial environment. Here, we report observations of the oxygen isotopic composition (Δ17O) of sulfate aerosol collected in the remote marine boundary layer (MBL) in spring and summer in order to evaluate sulfate production mechanisms in pristine-like environments. Model-aided analysis of the observations suggests that 33-50 % of sulfate in the MBL is formed via oxidation by hypohalous acids (HOX = HOBr + HOCl), a production mechanism typically excluded in large-scale models due to uncertainties in the reaction rates, which are due mainly to uncertainties in reactive halogen concentrations. Based on the estimated fraction of sulfate formed via HOX oxidation, we further estimate that daily-averaged HOX mixing ratios on the order of 0.01-0.1 parts per trillion (ppt = pmol/mol) in the remote MBL during spring and summer are sufficient to explain the observations.

  13. Cryo-transmission electron microscopy imaging of the morphology of submicrometer aerosol containing organic acids and ammonium sulfate.

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    Veghte, Daniel P; Bittner, Danielle Rae; Freedman, Miriam Arak

    2014-03-04

    The effects of aerosol particles on heterogeneous atmospheric chemistry and climate are determined in part by the internal arrangement of compounds within the particles. To characterize the morphology of internally mixed aerosol particles in the accumulation mode size regime, we have used cryo-transmission electron microscopy to investigate the phase separation behavior of dry, submicrometer particles composed of ammonium sulfate mixed with carboxylic acids (adipic, azelaic, citric, glutaric, malonic, pimelic, suberic, and succinic acid). Determining the morphology of dry particles is important for understanding laboratory studies of aerosol optical properties, reactivity, and cloud condensation nucleus activity, results from field instruments where aerosol particles are dried prior to analysis, and atmospheric processes like deposition mode heterogeneous ice nucleation that occur on dried particles. We observe homogeneous morphologies for highly soluble organic compounds. For organic compounds with limited aqueous solubility, partially engulfed structures are observed. At intermediate aqueous solubilities, small particles are homogeneous and larger particles are partially engulfed. Results are compared to previous studies of liquid-liquid phase separation in supermicrometer particles and the impact of these dry particle morphologies on aerosol-climate interactions are discussed.

  14. Acidic aerosol in urban air

    Energy Technology Data Exchange (ETDEWEB)

    Fukuda, M.; Yamaoka, S.; Miyazaki, T.; Oka, M.

    1982-01-01

    The distribution and chemical composition of acidic aerosol in Osaka City were investigated. Samples were collected at five sites in the city from June to September, 1979. Acidic aerosol was determined by the acid-base titration method, sulfate ion by barium chloride turbidimetry, nitrate ion by the xylenol method, and chloride ion by the mercury thiocyanate method. The concentration of acidic aerosol at five sites ranged from 7.7 micrograms per cubic meter to 10.0 micrograms per cubic meter, but mean concentrations in the residential area were slightly higher than those in the industrial area. When acidic aerosol concentrations were compared with concentrations of sulfate, nitrate, and chloride ions, a significant correlation was found between acidic aerosol and sulfate ion. The sum of the ion equivalents of the three types showed good correlation with the acidic aerosol equivalent during the whole period.

  15. Raman Spectra and Nucleation Rates of Sulfuric Acid and Ammonium Sulfate Aerosols Supercooled with Respect to Ice

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    Knopf, D. A.; Koop, T.; Weers, U. G.; Krieger, U. K.; Peter, T.

    2001-12-01

    Sulfuric acid and ammonium sulfate aerosol particles can serve as ice condensation nuclei for the formation of upper tropospheric cirrus clouds. These clouds influence the global radiation budget by scattering of short wavelength (solar) radiation as well as by absorbing long wavelength (terrestrial) radiation. Knowledge of the thermodynamics and the nucleation rates of aerosols is fundamental for the understanding of formation processes of cirrus clouds. Here, we present a new investigation tool to observe phase transitions of aerosols supercooled with respect to ice. Confocal Raman microscopy is used to determine the phase changes and the morphology of the particles. Raman spectroscopy is employed to distinguish and to characterize the different phases inside the frozen particles. Single droplets with a diameter of typically 20-120 μ m are deposited on a hydrophobically coated Herasil-plate that is covered by a spacer and another plate. Since the gas phase volume of the cell is small compared to the liquid droplet volume the composition of the droplets remains fixed during temperature changes. The temperature of the droplets can be varied between 150-350~K. We present the first Raman spectra of aqueous H2SO4/H2O and (NH4)2SO4/H2O droplets for several concentrations and temperatures to the homogeneous ice nucleation limits. The analysis of the speciation of the components inside the droplets (e.g. sulfate vs. bisulfate ions) is compared to results from thermodynamic models. Evaluation of the freezing data gives upper limits for ice nucleation rates of droplets as a function of sulfuric acid or ammonium sulfate concentration.

  16. Formation of the natural sulfate aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Kerminen, V.M.; Hillamo, R.; Maekinen, M.; Virkkula, A.; Maekelae, T.; Pakkanen, T. [Helsinki Univ. (Finland). Dept. of Physics

    1996-12-31

    Anthropogenic sulfate aerosol, together with particles from biomass burning, may significantly reduce the climatic warming due to man-made greenhouse gases. The radiative forcing of aerosol particles is based on their ability to scatter and absorb solar radiation (direct effect), and on their influences on cloud albedos and lifetimes (indirect effect). The direct aerosol effect depends strongly on the size, number and chemical composition of particles, being greatest for particles of 0.1-1 {mu}m in diameter. The indirect aerosol effect is dictated by the number of particles being able to act as cloud condensation nuclei (CCN). For sulfate particles, the minimum CCN size in tropospheric clouds is of the order of 0.05-0.2 {mu}m. To improve aerosol parameterizations in future climate models, it is required that (1) both primary and secondary sources of various particle types will be characterized at a greater accuracy, and (2) the influences of various atmospheric processes on the spatial and temporal distribution of these particles and their physico-chemical properties are known much better than at the present. In estimating the climatic forcing due to the sulfate particles, one of the major problems is to distinguish between sulfur from anthropogenic sources and that of natural origin. Global emissions of biogenic and anthropogenic sulfate pre-cursors are comparable in magnitude, but over regional scales either of these two source types may dominate. The current presentation is devoted to discussing the natural sulfate aerosol, including the formation of sulfur-derived particles in the marine environment, and the use of particulate methanesulfonic acid (MSA) as a tracer for the natural sulfate

  17. Spectral signatures of polar stratospheric clouds and sulfate aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massie, S.T.; Bailey, P.L.; Gille, J.C. [National Center for Atmospheric Research, Boulder, CO (United States); Lee, E.C. [Princeton Univ., NJ (United States); Mergenthaler, J.L.; Roche, A.E.; Kumer, J.B. [Lockheed Palo Alto Research Lab., CA (United States); Fishbein, E.F.; Waters, J.W. [California Institute of Technology, Pasadena, CA (United States); Lahoz, W.A. [Univ. of Reading (United Kingdom)

    1994-10-15

    Multiwavelength observations of Antarctic and midlatitude aerosol by the Cryogenic Limb Array Etalon Spectrometer (CLAES) experiment on the Upper Atmosphere Research Satellite are used to demonstrate a technique that identifies the location of polar stratospheric clouds. The technique discussed uses the normalized area of the triangle formed by the aerosol extinctions at 925, 1257, and 1605 cm{sup {minus}1} (10.8, 8.0, and 6.2 {mu}m) to derive a spectral aerosol measure M of the aerosol spectrum. Mie calculations for spherical particles and T-matrix calculations for spheroidal particles are used to generate theoretical spectral extinction curves for sulfate and polar stratospheric cloud particles. The values of the spectral aerosol measure M for the sulfate and polar stratospheric cloud particles are shown to be different. Aerosol extinction data, corresponding to temperatures between 180 and 220 K at a pressure of 46 hPa (near 21-km altitude) for 18 August 1992, are used to demonstrate the technique. Thermodynamic calculations, based upon frost-point calculation and laboratory phase-equilibrium studies of nitric acid trihydrate, are used to predict the location of nitric acid trihydrate cloud particles. 47 refs., 22 figs., 3 tabs.

  18. Heterogenous uptake of gaseous N(sub 2)O(sub 5) by sulfate aerosols

    Science.gov (United States)

    Leu, M. -T.; Kane, S. M.; Caloz, F.

    2001-01-01

    The heterogeneous uptake of gaseous N sub 2 O sub 5 by ammonium sulfate, ammonium bisulfate, and sulfuric acid aerosols as a function of relative humididty has been investigated at room temperature and atmsopheric pressure.

  19. Sensitivity studies for incorporating the direct effect of sulfate aerosols into climate models

    Science.gov (United States)

    Miller, Mary Rawlings Lamberton

    2000-09-01

    Aerosols have been identified as a major element of the climate system known to scatter and absorb solar and infrared radiation, but the development of procedures for representing them is still rudimentary. This study addresses the need to improve the treatment of sulfate aerosols in climate models by investigating how sensitive radiative particles are to varying specific sulfate aerosol properties. The degree to which sulfate particles absorb or scatter radiation, termed the direct effect, varies with the size distribution of particles, the aerosol mass density, the aerosol refractive indices, the relative humidity and the concentration of the aerosol. This study develops 504 case studies of altering sulfate aerosol chemistry, size distributions, refractive indices and densities at various ambient relative humidity conditions. Ammonium sulfate and sulfuric acid aerosols are studied with seven distinct size distributions at a given mode radius with three corresponding standard deviations implemented from field measurements. These test cases are evaluated for increasing relative humidity. As the relative humidity increases, the complex index of refraction and the mode radius for each distribution correspondingly change. Mie theory is employed to obtain the radiative properties for each case study. The case studies are then incorporated into a box model, the National Center of Atmospheric Research's (NCAR) column radiation model (CRM), and NCAR's community climate model version 3 (CCM3) to determine how sensitive the radiative properties and potential climatic effects are to altering sulfate properties. This study found the spatial variability of the sulfate aerosol leads to regional areas of intense aerosol forcing (W/m2). These areas are particularly sensitive to altering sulfate properties. Changes in the sulfate lognormal distribution standard deviation can lead to substantial regional differences in the annual aerosol forcing greater than 2 W/m 2. Changes in the

  20. Controlled exposures of human volunteers to sulfate aerosols. Health effects and aerosol characterization.

    Science.gov (United States)

    Avol, E L; Jones, M P; Bailey, R M; Chang, N M; Kleinman, M T; Linn, W S; Bell, K A; Hackney, J D

    1979-08-01

    Our laboratory has undertaken the study of possible acute adverse health effects of sulfate aerosols through controlled exposures of volunteer human subjects. Both healthy and asthmatic adult men were exposed for 2-hour periods (with intermittent exercise) to ammonium sulfate, ammonium bisulfate, and sulfuric acid of particle size distributions and concentrations intended to simulate "worst case" exposures during Los Angeles smog episodes. Lung function tests were performed by the subjects on entering and before exiting from a carefully controlled environmental chamber. Subject symptoms were evluated in a standardized manner. Aerosol concentrations and size distributions were determined by an on-line computer/aerometric monitoring system; gravimetric and chemical analyses were performed on impactor and total filter samples after test exposures. We found little or no evidence of adverse health effects from 2-hour multiple-day exposures to any of the compounds at "worst case" ambient concentrations.

  1. The influence of cloud droplet heterogeneity on sulfate production mechanisms constrained by isotopic measurements of sulfate aerosol

    Science.gov (United States)

    Alexander, B.; Allman, D. J.; Amos, H. M.; Fairlie, T. D.; Dachs, J.; Hegg, D.; Sletten, R. S.

    2011-12-01

    results in global increases in sulfate concentrations and aerosol acidity in the marine boundary layer compared to a bulk cloud pH calculation.

  2. Parameterization of the Optical Properties of Sulfate Aerosols.

    Science.gov (United States)

    Li, J.; Wong, J. G. D.; Dobbie, J. S.; Chýlek, P.

    2001-01-01

    Parameterizations of the shortwave optical properties of ammonium sulfate [(NH4)2SO4], ammonium bisulfate (NH4HSO4), and sulfuric acid (H2SO4) are provided as functions of relative humidity for high and low spectral resolution band models. The optical property parameterization is simple in form and in its dependence on relative humidity. The growth of the aerosol particles is based on equilibrium saturation theory, and the optical properties are computed from Mie theory. The optical properties necessary for the most commonly used radiative transfer methods are provided.Results show that when relative humidity effects are included in the backscatter fraction the radiative forcing is found to be a more sensitive function of near infrared wavelengths compared to visible wavelengths. For increasing relative humidity, sulfuric acid is found to have a larger effect on radiative forcing compared to the forcing by ammonium sulfate or ammonium bisulfate. Also, as relative humidity increases, forcing increases to higher values for smaller mode size distributions compared to forcing by larger mode distributions. These parameterizations will enable climate forcing studies to be performed with radiative transfer schemes that more accurately represent sulfate influences on the radiation balance.

  3. The role of sulfate aerosol in the formation of cloudiness over the sea

    Science.gov (United States)

    Aloyan, A. E.; Yermakov, A. N.; Arutyunyan, V. O.

    2016-07-01

    We estimate the impact of sulfate aerosols on cloudiness formation over the sea in the middle troposphere and the involvement of these particles in the formation of polar stratospheric clouds (PSCs) in the lower stratosphere. The first of these problems is solved using a combined model of moist convection and the formation of cloudiness and sulfate aerosols in the troposphere and lower stratosphere over the sea, incorporating natural emissions of sulfur-containing compounds. We have found that a significant source of condensation nuclei in the troposphere is the photochemical transformation of biogenic dimethyl sulfide (in addition to NaCl). The results of numerical experiments indicate that the absence of sulfate aerosols hinders the cloudiness formation over the sea in the middle and upper troposphere. The problem of sulfate aerosol involvement in the formation of supercooled ternary solutions (STSs) (PSC Type Ib) in the lower stratosphere is solved using a mathematical model of global transport of multicomponent gas pollutants and aerosols in the atmosphere. Using the combined model, numerical experiments were performed for the winter season in both hemispheres. Sulfate aerosols were found to really participate in the formation of STS particles. Without their participation, the formation of STS particles in the lower stratosphere would be hindered. We present the results of numerical calculations and discuss the distribution of concentrations of gaseous nitric and sulfuric acids, as well as mass concentrations of these components in STS particles.

  4. Reversible and irreversible processing of biogenic olefins on acidic aerosols

    OpenAIRE

    J. Liggio; Li, S.-M.

    2007-01-01

    Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton tran...

  5. Why Is the Climate Forcing of Sulfate Aerosols So Uncertain?

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Sulfate aerosol particles have strong scattering effect on the solar radiation transfer which results in increasing the planet albedo and, hence, tend to cool the earth-atmosphere system. Also, aerosols can act as the cloud condensation nuclei (CCN) which tend to increase the albedo of clouds and cool the global warming. The ARPEGE-Climat version 3 AGCM with FMR radiation scheme is used to estimate the direct and indirect radiative forcing of sulfate aerosols. For minimizing the uncertainties in assessing this kind of cooling effect, all kinds of factors are analyzed which have been mixed in the assessment process and may lead to the different results of the radiative forcing of aerosols. It is noticed that one of the uncertainties to assess the climate forcing of aerosols by GCM results from the different definition of radiative forcing that was used. In order to clarify this vague idea, the off-line case for considering no feedbacks and on-line case for including all the feedbacks have been used for assessment. The direct forcing of sulfate aerosols in off-line case is -0.57 W/m2 and -0.38 W/m2 for the clear sky and all sky respectively. The value of on-line case appears to be a little larger than that in off-line case chiefly due to the feedback of clouds. The indirect forcing of sulfate aerosols in off-line case is -1.4 W / m2 and -1.0 W / m2 in on-line case. The radiative forcing of sulfate aerosols has obvious regional characteristics. There is a larger negative radiative forcing over North America, Europe and East Asia. If the direct and indirect forcing are added together, it is enough to offset the positive radiative forcing induced by the greenhouse gases in these regions.

  6. Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

    Directory of Open Access Journals (Sweden)

    B. Jing

    2015-08-01

    Full Text Available Water soluble organic compounds (WSOCs are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, water uptake behavior of internally mixed WSOC aerosols remains limited characterization. Here, the hygroscopic properties of single component such as levoglucosan, oxalic acid, malonic acid, succinic acid and phthalic acid and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA. The coexisting hygroscopic species including levoglucosan, malonic acid and phthalic acid have strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppress its crystallization completely. The interactions between oxalic acid and levoglucosan are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM with UNIFAC method and Zdanovskii–Stokes–Robinson (ZSR approach increase at medium and high relative humidity (RH assuming oxalic acid in a solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH due to positive chemical interactions between solutes. Organic mixture has more complex effect on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan accounts for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake under high RH conditions and thus affect the cloud condensation nuclei (CCN activity, optical properties and chemical reactivity of

  7. Parameterization of the Optical Properties of Sulfate Aerosols in the Infrared.

    Science.gov (United States)

    Li, J.; Min, Qilong

    2002-11-01

    Parameterizations of absorptance depth for ammonium sulfate [(NH4)2SO4], ammonium bisulfate (NH4HSO4), and sulfuric acid (H2SO4) in the infrared are provided for an eight-band model (covering 340-2500 cm1) and for 32 individual wavenumbers in order to generate other band schemes. The parameterization is simple in form and in its dependence on relative humidity.It is found that the aerosol surface infrared forcing can cancel about 12%-24% aerosol surface solar forcing in a clear sky condition. Also the existence of clouds could enhance the ratio of aerosol surface infrared forcing to the aerosol surface solar forcing. In contrast to the solar case, a small mode size distribution does not always produce a larger aerosol surface forcing. Also it is found that the aerosol surface forcing is dependent on the aerosol location. Very simple analysis is presented to help understand the related physics on sulfate aerosol infrared radiative forcing.

  8. Effective Henry's law partitioning and the salting constant of glyoxal in aerosols containing sulfate.

    Science.gov (United States)

    Kampf, Christopher J; Waxman, Eleanor M; Slowik, Jay G; Dommen, Josef; Pfaffenberger, Lisa; Praplan, Arnaud P; Prévôt, André S H; Baltensperger, Urs; Hoffmann, Thorsten; Volkamer, Rainer

    2013-05-07

    The reversible partitioning of glyoxal was studied in simulation chamber experiments for the first time by time-resolved measurements of gas-phase and particle-phase concentrations in sulfate-containing aerosols. Two complementary methods for the measurement of glyoxal particle-phase concentrations are compared: (1) an offline method utilizing filter sampling of chamber aerosols followed by HPLC-MS/MS analysis and (2) positive matrix factorization (PMF) analysis of aerosol mass spectrometer (AMS) data. Ammonium sulfate (AS) and internally mixed ammonium sulfate/fulvic acid (AS/FA) seed aerosols both show an exponential increase of effective Henry's law coefficients (KH,eff) with AS concentration (cAS, in mol kg(-1) aerosol liquid water, m = molality) and sulfate ionic strength, I(SO4(2-)) (m). A modified Setschenow plot confirmed that "salting-in" of glyoxal is responsible for the increased partitioning. The salting constant for glyoxal in AS is K(S)CHOCHO = (-0.24 ± 0.02) m(-1), and found to be independent of the presence of FA. The reversible glyoxal uptake can be described by two distinct reservoirs for monomers and higher molecular weight species filling up at characteristic time constants. These time constants are τ1 ≈ 10(2) s and τ2 ≈ 10(4) s at cAS < 12 m, and about 1-2 orders of magnitude slower at higher cAS, suggesting that glyoxal uptake is kinetically limited at high salt concentrations.

  9. Transient Sulfate Aerosols as a Signature of Exoplanet Volcanism

    CERN Document Server

    Misra, Amit; Koehler, Matthew C; Sholes, Steven

    2015-01-01

    Geological activity is thought to be important for the origin of life and for maintaining planetary habitability. We show that transient sulfate aerosols could be a signature of exoplanet volcanism, and therefore a geologically active world. A detection of transient aerosols, if linked to volcanism, could thus aid in habitability evaluations of the exoplanet. On Earth, subduction-induced explosive eruptions inject SO2 directly into the stratosphere, leading to the formation of sulfate aerosols with lifetimes of months to years. We demonstrate that the rapid increase and gradual decrease in sulfate aerosol loading associated with these eruptions may be detectable in transit transmission spectra with future large-aperture telescopes, such as the James Webb Space Telescope (JWST) and European Extremely-Large Telescope (E-ELT) for a planetary system at a distance of 10 pc, assuming an Earth-like atmosphere, bulk composition, and size. Specifically, we find that a S/N of 12.1 and 7.1 could be achieved with E-ELT (...

  10. Measuring 35S of Aerosol Sulfate: Techniques and First Results

    Science.gov (United States)

    Brothers, L. A.; Dominguez, G.; Bluen, B.; Corbin, A.; Abramian, A.; Thiemens, M. H.

    2007-12-01

    On a global and regional level, the cycling of sulfur in the environment has consequences for air quality, human health, and may contribute to global climate change. Due to its multiple oxidation states, the sulfur cycle is very complex and poorly understood. Stable isotopes are currently used to understand reaction pathways as well as sources and sinks of sulfurous compounds in the environment. Sulfur also has one short lived (τ1/2 ~87 d) radioactive isotope (35S) which is continuously made in the atmosphere by the cosmic ray spallation of argon, is then quickly oxidized to 35SO2 and enters the atmospheric sulfur cycle. The short-lived radioactive nature of this isotope of sulfur provides us with potentially powerful tracer for understanding the time scales at which sulfur is oxidized, deposited, and transported in the atmosphere and the deposition of atmospheric sulfate into rivers and water catchments. However, despite its potential, the use of 35S as a tracer of aerosol chemistry has not been fully exploited, Here we present details of instrumental set up for measuring 35S in aerosol sulfate and some preliminary results of measurements of 35S abundances in aerosols from Riverside (inland) and La Jolla (coastal) CA and discuss the sensitivity and limitations of the measurements in providing insights into day/night aerosol chemistry (Riverside) as well as the uptake of SO2 pollution in coastal environments by sea-salt aerosols. Also, we present preliminary results from measurement of sulfate in river water in Ecuador before and after precipitation events.

  11. Comparative irritant potency of inhaled sulfate aerosols--effects on bronchial mucociliary clearance.

    Science.gov (United States)

    Schlesinger, R B

    1984-08-01

    The effect of 1-hr oral inhalation exposures to submicrometer aerosols of ammonium bisulfate (NH4HSO4), ammonium sulfate [NH4)2SO4), and sodium sulfate (Na2SO4) upon mucociliary clearance from the bronchial tree of rabbits was examined. Exposures to NH4HSO4 at concentrations of approximately 600-1700 micrograms/m3 produced a significant depression of clearance rate only at the highest exposure level. No significant effects were observed with the other sulfates at levels up to approximately 2000 micrograms/m3. When results were compared to those from another study in this laboratory using sulfuric acid (H2SO4) aerosol, the ranking of irritant potency was H2SO4 greater than NH4HSO4 greater than (NH4)2SO4, Na2SO4. Alteration in bronchial mucociliary clearance due to sulfate aerosols appears to be related to the deposition of [H+] on the mucus lining of conducting airways.

  12. Light absorption by secondary organic aerosol from α-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    Energy Technology Data Exchange (ETDEWEB)

    Song, Chen [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Now at R. J. Reynolds Tobacco Company, Winston-Salem North Carolina USA; Gyawali, Madhu [Department of Physics, University of Nevada Reno, Nevada System of Higher Education, Reno Nevada USA; Now at Desert Research Institute, Nevada System of Higher Education, Reno Nevada USA; Zaveri, Rahul A. [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Shilling, John E. [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Arnott, W. Patrick [Department of Physics, University of Nevada Reno, Nevada System of Higher Education, Reno Nevada USA

    2013-10-25

    It is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark α-pinene + O3 and α-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from α-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Finally and overall, these results suggest that dark α-pinene + O3 and α-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  13. Heterogeneous Uptake of Gaseous N2O5 by Sulfate Aerosols

    Science.gov (United States)

    Leu, M.; Kane, S. M.; Caloz, F.

    2001-12-01

    The heterogeneous uptake of gaseous N2O5 by ammonium sulfate [(NH4)2SO4], ammonium bisulfate [NH4HSO4], and sulfuric acid [H2SO4] aerosols as a function of relative humidity has been investigated at room temperature and atmospheric pressure. Ammonium-containing aerosols were generated by a constant output atomizer and conditioned by passing through a diffusion dryer. Sulfuric acid aerosols were produced by the homogeneous reaction of SO3 and H2O in a borosilicate vessel. Addition of a dry or wet N2 flow controlled the relative humidity (RH) of these aerosol flows. Using a chemical ionization mass spectrometer (CIMS) for N2O5 concentration monitoring and a scanning mobility particle spectrometer (SMPS) for aerosol characterization, reaction probabilities (g) in the range of 0.001 to 0.1 for the uptake of N2O5 were determined as a function of RH. The results are expressed as follows: gamma[(NH4)2SO4] = 2.79 x 10-4 + 1.30 x 10-4 x (RH) -3.43 x 10-6 x (RH)2 + 7.52 x 10-8 x (RH)3, gamma[NH4HSO4] = 2.07 x 10-3 - 1.48 x 10-4 x (RH) + 8.26 x 10-6 x (RH)2, and gamma[H2SO4] = 0.052 - 2.79 x 10-4 x (RH) . We suggest that the water content and phase in the ammonium-containing aerosols control the reactivity of N2O5 while liquid-phase ionic reactions primarily dominate the uptake in sulfuric acid aerosols.

  14. Amino acids in Arctic aerosols

    Directory of Open Access Journals (Sweden)

    E. Scalabrin

    2012-11-01

    Full Text Available Amino acids are significant components of atmospheric aerosols, affecting organic nitrogen input to marine ecosystems, atmospheric radiation balance, and the global water cycle. The wide range of amino acid reactivities suggest that amino acids may serve as markers of atmospheric transport and deposition of particles. Despite this potential, few measurements have been conducted in remote areas to assess amino acid concentrations and potential sources. Polar regions offer a unique opportunity to investigate atmospheric processes and to conduct source apportionment studies of such compounds. In order to better understand the importance of amino acid compounds in the global atmosphere, we determined free amino acids (FAAs in seventeen size-segregated aerosol samples collected in a polar station in the Svalbard Islands from 19 April until 14 September 2010. We used an HPLC coupled with a tandem mass spectrometer (ESI-MS/MS to analyze 20 amino acids and quantify compounds at fmol m−3 levels. Mean total FAA concentration was 1070 fmol m−3 where serine and glycine were the most abundant compounds in almost all samples and accounted for 45–60% of the total amino acid relative abundance. The other eighteen compounds had average concentrations between 0.3 and 98 fmol m−3. The higher amino acid concentrations were present in the ultrafine aerosol fraction (< 0.49 μm and accounted for the majority of the total amino acid content. Local marine sources dominate the boreal summer amino acid concentrations, with the exception of the regional input from Icelandic volcanic emissions.

  15. Amino acids in Arctic aerosols

    Directory of Open Access Journals (Sweden)

    E. Scalabrin

    2012-07-01

    Full Text Available Amino acids are significant components of atmospheric aerosols, affecting organic nitrogen input to marine ecosystems, atmospheric radiation balance, and the global water cycle. The wide range of amino acid reactivities suggest that amino acids may serve as markers of atmospheric transport and deposition of particles. Despite this potential, few measurements have been conducted in remote areas to assess amino acid concentrations and potential sources. Polar regions offer a unique opportunity to investigate atmospheric processes and to conduct source apportionment studies of such compounds. In order to better understand the importance of amino acid compounds in the global atmosphere, we determined free amino acids (FAAs in seventeen size-segregated aerosol samples collected in a polar station in the Svalbard Islands from 19 April until 14 September 2010. We used an HPLC coupled with a tandem mass spectrometer (ESI-MS/MS to analyze 20 amino acids to quantify compounds at fmol m−3 levels. Mean total FAA concentration was 1070 fmol m−3 where serine and glycine were the most abundant compounds in almost all samples and accounted for 45–60% of the total amino acid relative abundance. The other eighteen compounds had average concentrations between 0.3 and 98 fmol m−3. The higher amino acid concentrations were present in the ultrafine aerosol fraction (<0.49 μm and accounted for the majority of the total amino acid content. Local marine sources dominate the boreal summer amino acid concentrations, with the exception of the regional input from Icelandic volcanics.

  16. Effects of brief and intermediate exposures to sulfate submicron aerosols and sulfate injections on cardiopulmonary function of dogs and tracheal mucous velocity of sheep

    Energy Technology Data Exchange (ETDEWEB)

    Sackner, M.A. (Mount Sinai Medical Center, Miami Beach, FL); Dougherty, R.L.; Chapman, G.A.; Cipley, J.; Perez, D.; Kwoka, M.; Reinhart, M.; Brito, M.; Schreck, R.

    1981-06-01

    Pulmonary mechanics of anesthetized dogs were not changed or were minimally altered by breathing the following compounds as submicron aerosols in concentrations up to 17.3 mg/m/sup 3/ for 7.5 min: (1) sodium chloride (as a control), (2) sodium sulfate, (3) ammonium sulfate, (4) zinc sulfate, (5) zinc ammonium sulfate, (6) ammonium bisulfate, (7) aluminum sulfate, (8) manganese sulfate, (9) nickel sulfate, (10) copper sulfate, (11) ferrous fulfate, and (12) ferric sulfate. Submicron aerosols of these compounds in concentrations of 4.1 to 8.8 mg/m/sup 3/, administered for 4 h to anesthetized dogs, did not affect mechanics of breathing, hemodynamics, and arterial blood gases. In conscious sheep, tracheal mucous velocity was not altered by exposure to the submicron aerosols of the sulfate compounds. None of these compounds, injected iv in a dose of 1 mg, had adverse effects on mechanics of breathing, pulmonary and systemic hemodynamics, or arterial blood gases. In 100-mg injections, zinc sulfate and zinc ammonium sulfate produced a fall in cardiac output, systemic hypotension, hypoxemia, and metabolic acidosis. Copper sulfate at this dose produced pulmonary hypertension, a fall in cardiac output, hypoxemia, respiratory acidosis, and a decrease of specific total respiratory conductance. It is concluded that submicron aerosols of sulfate salts do not have adverse cardiopulmonary effects when administered in high concentrations for up to 4 h. However, prolonged exposure to high concentrations of zinc sulfate, zinc ammonium sulfate, and copper sulfate aerosols might have adverse cardiopulmonary effects.

  17. Continuous Monitoring of Nitrate and Sulfate in Aerosols with Microchip Electrophoresis

    Science.gov (United States)

    Noblitt, S. D.; Henry, C. S.; Collett, J. L.; Hering, S. V.

    2007-12-01

    Routine monitoring of aerosol composition is important since aerosols can negatively affect both the environment and health. Water-soluble inorganic ions are commonly monitored using the particle-into-liquid-sampler coupled to ion chromatography (PILS-IC). However, a less-expensive, faster, and more portable analysis system is desirable. Here, we present the coupling of microchip capillary electrophoresis (MCE) to a water-based condensation particle counter (WCPC) for rapid and continuous monitoring of chloride, nitrate, and sulfate in atmospheric aerosols. To achieve a working system, several obstacles were overcome. A working interface between the electrophoresis microchip and the WCPC sampler was developed. This interface was designed to remove insoluble particles from the analysis stream and to prevent the sampling-induced pressure gradient from altering flow in the microfluidic device. The electrophoresis separation chemistry was optimized for the small chip size, to be free from potential interfering compounds, and to operate continuously for several hours. In-field performance of the integrated system was tested with ambient aerosols. Anion analyses can be performed in less than two minutes with aerosol detection limits similar to the PILS-IC, but with greater portability and reduced cost. Coupling microfluidic devices to aerosol sampling technology proves successful for inorganic anion analysis and shows potential for faster and more sensitive measurements as well as monitoring of other water- soluble aerosol components such as organic acids, cations, and carbohydrates. The reduced cost and size relative to current technology indicate that greater deployment of monitoring stations or the advent of portable analyzers may be feasible.

  18. An exploratory study of alkali sulfate aerosol formation during biomass combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti; Frandsen, Flemming; Livbjerg, Hans;

    2008-01-01

    It is still in discussion to what extent alkali sulfate aerosols in biomass combustion are formed in the gas phase by a homogeneous mechanism or involve heterogeneous or catalyzed reactions. The present study investigates sulfate aerosol formation based on calculations with a detailed gas phase...... mechanism. The modeling predictions are compared to data from laboratory experiments and entrained flow reactor experiments available in the literature. The analysis support that alkali sulfate aerosols are formed from homogeneous nucleation following a series of steps occurring in the gas phase. The rate...

  19. Effective Henry's Law constant measurements for glyoxal in model aerosols containing sulfate

    Science.gov (United States)

    Kampf, C.; Waxman, E.; Slowik, J.; Dommen, J.; Prevot, A.; Baltensperger, U.; Noziere, B.; Hoffmann, T.; Volkamer, R.

    2012-04-01

    Traditional models represent secondary organic aerosol (SOA) formation based on the gas-phase oxidation of a limited set of precursor molecules. However, these models tend to under-estimate the amounts and degree of oxygenation of actual SOA, indicating missing processes. One such source that has become increasingly important in recent years is glyoxal (CHOCHO, the smallest alpha-dicarbonyl). Unlike traditional SOA precursors, glyoxal forms SOA by partitioning to the aqueous phase according to Henry's Law. This work presents an analysis of Henry's Law constants for glyoxal uptake to laboratory-generated aerosols in a dynamically coupled gas-aerosol system. We combine CU LED-CE-DOAS measurements of gas-phase glyoxal with online HR-Tof-AMS and time-resolved HPLC ESI MS/MS particle-phase measurements to characterize the time resolved evolution of glyoxal partitioning, and relate molecular-specific measurements to AMS mass spectra. The experiments were performed in the simulation chamber facility at PSI, Switzerland, and investigate ammonium sulfate (AS), and mixed AS / fulvic acid seed aerosols under relative humidity conditions ranging from 50 to 85% RH. The Henry's Law and effective Henry's Law constants are compared with other values reported in the literature.

  20. Effects of the physical state of tropospheric ammonium-sulfate-nitrate particles on global aerosol direct radiative forcing

    Directory of Open Access Journals (Sweden)

    S. T. Martin

    2004-01-01

    Full Text Available The effect of aqueous versus crystalline sulfate-nitrate-ammonium tropospheric particles on global aerosol direct radiative forcing is assessed. A global three-dimensional chemical transport model predicts sulfate, nitrate, and ammonium aerosol mass. An aerosol thermodynamics model is called twice, once for the upper side (US and once for lower side (LS of the hysteresis loop of particle phase. On the LS, the sulfate mass budget is 40% solid ammonium sulfate, 12% letovicite, 11% ammonium bisulfate, and 37% aqueous. The LS nitrate mass budget is 26% solid ammonium nitrate, 7% aqueous, and 67% gas-phase nitric acid release due to increased volatility upon crystallization. The LS ammonium budget is 45% solid ammonium sulfate, 10% letovicite, 6% ammonium bisulfate, 4% ammonium nitrate, 7% ammonia release due to increased volatility, and 28% aqueous. LS aerosol water mass partitions as 22% effloresced to the gas-phase and 78% remaining as aerosol mass. The predicted US/LS global fields of aerosol mass are employed in a Mie scattering model to generate global US/LS aerosol optical properties, including scattering efficiency, single scattering albedo, and asymmetry parameter. Global annual average LS optical depth and mass scattering efficiency are, respectively, 0.023 and 10.7 m2 (g SO4-2-1, which compare to US values of 0.030 and 13.9 m2 (g SO4-2-1. Radiative transport is computed, first for a base case having no aerosol and then for the two global fields corresponding to the US and LS of the hysteresis loop. Regional, global, seasonal, and annual averages of top-of-the-atmosphere aerosol radiative forcing on the LS and US (FL and FU, respectively, in W m-2 are calculated. Including both anthropogenic and natural emissions, we obtain global annual averages of FL=-0.750, FU=-0.930, and DFU,L=24% for full sky calculations without clouds and FL=-0.485, FU=-0.605, and DFU,L=25% when clouds are included. Regionally, DFU,L=48% over the USA, 55% over Europe

  1. Simulation of nitrate, sulfate, and ammonium aerosols over the United States

    Directory of Open Access Journals (Sweden)

    J. M. Walker

    2012-11-01

    Full Text Available Atmospheric concentrations of inorganic gases and aerosols (nitrate, sulfate, and ammonium are simulated for 2009 over the United States using the chemical transport model GEOS-Chem. Predicted aerosol concentrations are compared with surface-level measurement data from the Interagency Monitoring of Protected Visual Environments (IMPROVE, the Clean Air Status and Trends Network (CASTNET, and the California Air Resources Board (CARB. Sulfate predictions nationwide are in reasonably good agreement with observations, while nitrate and ammonium are over-predicted in the East and Midwest, but under-predicted in California, where observed concentrations are the highest in the country. Over-prediction of nitrate in the East and Midwest is consistent with results of recent studies, which suggest that nighttime nitric acid formation by heterogeneous hydrolysis of N2O5 is over-predicted based on current values of the N2O5 uptake coefficient, γ, onto aerosols. After reducing the value of γ by a factor of 10, predicted nitrate levels in the US Midwest and East still remain higher than those measured, and over-prediction of nitrate in this region remains unexplained. Comparison of model predictions with satellite measurements of ammonia from the Tropospheric Emissions Spectrometer (TES indicates that ammonia emissions in GEOS-Chem are underestimated in California and that the nationwide seasonality applied to ammonia emissions in GEOS-Chem does not represent California very well, particularly underestimating winter emissions. An ammonia sensitivity study indicates that GEOS-Chem simulation of nitrate is ammonia-limited in southern California and much of the state, suggesting that an underestimate of ammonia emissions is likely the main cause for the under-prediction of nitrate aerosol in many areas of California. An approximate doubling of ammonia emissions is needed to reproduce observed nitrate concentrations in

  2. Reversible and irreversible processing of biogenic olefins on acidic aerosols

    Directory of Open Access Journals (Sweden)

    J. Liggio

    2008-04-01

    Full Text Available Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA; however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ether formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ were estimated for a fast initial uptake governed by the mass accommodation coefficient (α and ranged from 1×10-6-2.5×10-2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7-1×10-4. These processes may potentially lead to a considerable amount of SOA from the various biogenic hydrocarbons under acidic conditions, which can be highly significant for freshly nucleated aerosols, particularly given the large array of atmospheric olefins.

  3. Reversible and irreversible processing of biogenic olefins on acidic aerosols

    Science.gov (United States)

    Liggio, J.; Li, S.-M.

    2008-04-01

    Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ether formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ) were estimated for a fast initial uptake governed by the mass accommodation coefficient (α) and ranged from 1×10-6-2.5×10-2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7-1×10-4. These processes may potentially lead to a considerable amount of SOA from the various biogenic hydrocarbons under acidic conditions, which can be highly significant for freshly nucleated aerosols, particularly given the large array of atmospheric olefins.

  4. Particle size distribution and behavior of sulfate aerosols in a coastal region

    Energy Technology Data Exchange (ETDEWEB)

    Fujimura, M.; Hashimoto, Y.

    1979-01-01

    To obtain fundamental knowledge about sulfate aerosols, a field research was conducted in a coastal region distant from industrial pollution sources. The aerosol samples were analyzed for some elements, sulfate and ammonium ions. Sulfate was determined by the turbidimetry with 2-aminoperimidine, and ammonium was by the colorimetry of indophenol method. Trace elements with short-lived nuclides were analyzed by instrumental neutron activation analysis. The mass-size distribution curve of total aerosols was the general bimodal pattern, although the concentration level was very low. Most of sulfate and ammonium salts were distributed in the fine particle range less than 2 microns in aerodynamic diameter, but sulfate had another peak, thought to be of maritime origin, in the coarse particle range. Nevertheless, many fine sulfate particles that had been produced secondarily in the atmosphere were found in such a less polluted coastal region. The change of the sulfate concentrations obtained by the two-stage Andersen type sampler showed a correlation with the humidity. This may suggest that the formation of sulfate aerosols from sulfur dioxide could be related to a catalytic oxidation process in water drops.

  5. Sulfate and acid resistant concrete and mortar

    Science.gov (United States)

    Liskowitz, John W.; Wecharatana, Methi; Jaturapitakkul, Chai; Cerkanowicz, deceased, Anthony E.

    1998-01-01

    The present invention relates to concrete, mortar and other hardenable mixtures comprising cement and fly ash for use in construction and other applications, which hardenable mixtures demonstrate significant levels of acid and sulfate resistance while maintaining acceptable compressive strength properties. The acid and sulfate hardenable mixtures of the invention containing fly ash comprise cementitious materials and a fine aggregate. The cementitous materials may comprise fly ash as well as cement. The fine aggregate may comprise fly ash as well as sand. The total amount of fly ash in the hardenable mixture ranges from about 60% to about 120% of the total amount of cement, by weight, whether the fly ash is included as a cementious material, fine aggregate, or an additive, or any combination of the foregoing. In specific examples, mortar containing 50% fly ash and 50% cement in cementitious materials demonstrated superior properties of corrosion resistance.

  6. Detection of volcanic sulfate aerosol with Envisat MIPAS shown for the Kasatochi, Sarychev, and Nabro eruptions

    Science.gov (United States)

    Griessbach, Sabine; Hoffmann, Lars; Spang, Reinhold; von Hobe, Marc; Müller, Rolf; Riese, Martin

    2013-04-01

    Stratospheric sulfate aerosol is known to have a strong impact on climate. Transport pathways of sulfur dioxide and sulfate aerosol to the stratosphere are still discussed. It is known that volcanic eruptions can inject significant amounts of sulfur directly into the stratosphere. Most sulfur, however, is injected into the troposphere and only a fraction of it can make its way into the stratosphere. Global and altitude resolved time series of observations are a valuable source of information for sulfur dioxide and sulfate aerosol detection. Here we present a new aerosol detection method for the infrared limb sounder Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the results for the Kasatochi, Sarychev, and Nabro eruptions. The new detection method utilizes three infrared window regions that are located around 830, 960, and 1224 cm-1. The combination of these three windows allows for a better detection of enhanced aerosol events in the troposphere as well as the discrimination from ice clouds. With this new method the 10 year record of MIPAS measurements was analyzed. The most remarkable sulfate aerosol events follow the Kasatochi, Sarychev, and Nabro eruptions. After these eruptions enhanced aerosol is detected in the upper troposphere and lower stratosphere (UTLS) region. Within one to two months it spreads over most of the northern hemisphere. In the tropics the aerosol reaches altitudes up to around 20 km and in the Arctic up to 15 km. The enhanced aerosol signal can be observed for about 5, 7, and up to 10 month for the Kasatochi, Sarychev, and Nabro eruptions, respectively. During this period the enhanced aerosol detections decrease in number, strength, and observation altitude. After the Nabro eruption on 13 June 2011 volcanic aerosol is detected in the UTLS region two days after the initial eruption. The following days the aerosol moves around the northern edge of the Asian monsoon region, is then transported southwards and later

  7. Small volcanic eruptions and the stratospheric sulfate aerosol burden

    Science.gov (United States)

    Pyle, David M.

    2012-09-01

    Understanding of volcanic activity and its impacts on the atmosphere has evolved in discrete steps, associated with defining eruptions. The eruption of Krakatau, Indonesia, in August 1883 was the first whose global reach was recorded through observations of atmospheric phenomena around the world (Symons 1888). The rapid equatorial spread of Krakatau's ash cloud revealed new details of atmospheric circulation, while the vivid twilights and other optical phenomena were soon causally linked to the effects of particles and gases released from the volcano (e.g. Stothers 1996, Schroder 1999, Hamilton 2012). Later, eruptions of Agung, Bali (1963), El Chichón, Mexico (1982) and Pinatubo, Philippines (1991) led to a fuller understanding of how volcanic SO2 is transformed to a long-lived stratospheric sulfate aerosol, and its consequences (e.g. Meinel and Meinel 1967, Rampino and Self 1982, Hoffman and Rosen 1983, Bekki and Pyle 1994, McCormick et al 1995). While our ability to track the dispersal of volcanic emissions has been transformed since Pinatubo, with the launch of fleets of Earth-observing satellites (e.g. NASA's A-Train; ESA's MetOp) and burgeoning networks of ground-based remote-sensing instruments (e.g. lidar and sun-photometers; infrasound and lightning detection systems), there have been relatively few significant eruptions. Thus, there have been limited opportunities to test emerging hypotheses including, for example, the vexed question of the role of 'smaller' explosive eruptions in perturbations of the atmosphere—those that may just be large enough to reach the stratosphere (of size 'VEI 3', Newhall and Self 1982, Pyle 2000). Geological evidence, from ice-cores and historical eruptions, suggests that small explosive volcanic eruptions with the potential to transport material into the stratosphere should be frequent (5-10 per decade), and responsible for a significant proportion of the long-term time-averaged flux of volcanic sulfur into the stratosphere

  8. Reversible and irreversible processing of biogenic olefins on acidic aerosols

    Directory of Open Access Journals (Sweden)

    J. Liggio

    2007-08-01

    Full Text Available Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA; however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ester formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ were estimated for a fast initial uptake governed by the mass accommodation coefficient (α and ranged from 1×10-6–2.5×10−2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7–1×10-4. These processes are estimated to potentially produce greater than 2.5 μg m−3 of SOA from the various biogenic hydrocarbons under atmospheric conditions, which can be highly significant given the large array of atmospheric olefins.

  9. Acid Sulfate Alteration in Gusev Crater, Mars

    Science.gov (United States)

    Morris, R. V.; Ming, D. W.; Catalano, J. G.

    2016-01-01

    dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

  10. Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles

    Directory of Open Access Journals (Sweden)

    K. J. Baustian

    2010-03-01

    Full Text Available Heterogeneous ice nucleation on solid ammonium sulfate and glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation is highly selective and occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K an average ice saturation ratio of S = 1.10±0.07 for solid ammonium sulfate was observed. Over the same temperature range, S values observed for ice nucleation on glutaric acid particles increased from 1.2 at 235 K to 1.6 at 218 K. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus than glutaric acid. Our results suggest that heterogeneous nucleation on ammonium sulfate may be an important pathway for atmospheric ice nucleation and cirrus cloud formation when solid ammonium sulfate aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropical tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted.

  11. THE IMPACT OF RELATIVE HUMIDITY ON THE RADIATIVE PROPERTY AND RADIATIVE FORCING OF SULFATE AEROSOL

    Institute of Scientific and Technical Information of China (English)

    张立盛; 石广玉

    2001-01-01

    With the data of complex refractive index of sulfate aerosol, the radiative properties of the aerosol under 8 relative humidity conditions are calculated in this paper. By using the concentration distribution from two CTM models and LASG GOALS/AGCM, the radiative forcing due to hygroscopic sulfate aerosol is simulated. The results show that: (1) With the increase of relative humidity, the mass extinction coefficiency factor decreases in the shortwave spectrum: single scattering albedo keeps unchanged except for a little increase in longwave spectrum, and asymmetry factor increases in whole spectrum. (2) Larger differences occur in radiative forcing simulated by using two CTM data, and the global mean forcing is -0. 268 and -0. 816 W/m2,respectively. (3) When the impact of relative humidity on radiative property is taken into account,the distribution pattern of radiative forcing due to the wet particles is very similar to that of dry sulfate, but the forcing value decreases by 6%.

  12. Controls of Soluble Al in Experimental Acid Sulfate Conditions and Acid Sulfate Soils

    Institute of Scientific and Technical Information of China (English)

    LINCHUXIA; M.D.MELVILLE

    1997-01-01

    The controls of soluble Al concentration were examined in three situations of acid sulfate conditions:1) experimental acid sulfate conditions by addition of varying amounts of Al(OH)3(gibbsite) into a sequence of H2SO4 solutions;2)experimental acid sulfate conditions by addition of the same sequence of H2SO4 solutions into two non-cid sulfacte soil samples with known amounts of acid oxalate extractable Al; and 3) actual acid sulfate soil conditions.The experiment using gibbsite as an Al-bearing mineral showed that increase in the concentration of H2SO4 solution increased the soluble Al concentration,accompanied by a decrease i the solution pH, Increasing amount of gibbsite added to the H2SO4 solutions also increased soluble Al concentration,but resulted in an increase in solution pH.Within the H2SO4 concentration range of 0.0005-0.5mol L-1 and the Al(OH)3 range of 0.01-0.5g(in 25 mL of H2SO4 solutions),the input of H2SO4 had the major control on soluble Al Concentration and pH .The availability of Al(OH)3,however,was responsible for the spread fo the various sample points,with a tendency that the samples containing more gibbsite had a higher soluble Al concentration than those containing less gibbsite at equivalent pH levels.The experimental results from treatment of soil samples with H2SO4 solutions and the analytical results of acid sulfate soils also showed the similar trend.

  13. Evaporation of sulfate aerosols at low relative humidity

    Science.gov (United States)

    Tsagkogeorgas, Georgios; Roldin, Pontus; Duplissy, Jonathan; Rondo, Linda; Tröstl, Jasmin; Slowik, Jay G.; Ehrhart, Sebastian; Franchin, Alessandro; Kürten, Andreas; Amorim, Antonio; Bianchi, Federico; Kirkby, Jasper; Petäjä, Tuukka; Baltensperger, Urs; Boy, Michael; Curtius, Joachim; Flagan, Richard C.; Kulmala, Markku; Donahue, Neil M.; Stratmann, Frank

    2017-07-01

    Evaporation of sulfuric acid from particles can be important in the atmospheres of Earth and Venus. However, the equilibrium constant for the dissociation of H2SO4 to bisulfate ions, which is the one of the fundamental parameters controlling the evaporation of sulfur particles, is not well constrained. In this study we explore the volatility of sulfate particles at very low relative humidity. We measured the evaporation of sulfur particles versus temperature and relative humidity in the CLOUD chamber at CERN. We modelled the observed sulfur particle shrinkage with the ADCHAM model. Based on our model results, we conclude that the sulfur particle shrinkage is mainly governed by H2SO4 and potentially to some extent by SO3 evaporation. We found that the equilibrium constants for the dissociation of H2SO4 to HSO4-(KH2SO4) and the dehydration of H2SO4 to SO3 (xKSO3) are KH2SO4 = 2-4 × 109 mol kg-1 and xKSO3 ≥ 1.4 × 1010 at 288.8 ± 5 K.

  14. Genesis and solution chemistry of acid sulfate soils in Thailand

    NARCIS (Netherlands)

    Breemen, van N.

    1976-01-01

    To study short-term and long-term chemical processes in periodically flooded acid sulfate soils in the Bangkok Plain and in various smaller coastal plains along the Gulf of Thailand, 16 acid sulfate soils and one non-acid marine soil were examined for distribution of iron-sulfur compounds, elemental

  15. Genesis and solution chemistry of acid sulfate soils in Thailand

    NARCIS (Netherlands)

    Breemen, van N.

    1976-01-01

    To study short-term and long-term chemical processes in periodically flooded acid sulfate soils in the Bangkok Plain and in various smaller coastal plains along the Gulf of Thailand, 16 acid sulfate soils and one non-acid marine soil were examined for distribution of iron-sulfur compounds, elemental

  16. Uptake of Organic Vapors by Sulfate Aerosols: Physical and Chemical Processes

    Science.gov (United States)

    Michelsen, R. R.; Ashbourn, S. F. M.; Iraci, L.T.; Staton, S. J. R.

    2003-01-01

    While it is known that upper tropospheric sulfate particles contain a significant amount of organic matter, both the source of the organic fraction and its form in solution are unknown. These studies explore how the chemical characteristics of the molecules and surfaces in question affect heterogeneous interactions. The solubilities of acetaldehyde [CH3CHO] and ethanol [CH3CH20H] in cold, aqueous sulfuric acid solutions have been measured by Knudsen cell studies. Henry's law solubility coefficients range from 10(exp 2) to 10(exp 5) M/atm for acetaldehyde, and from 10(exp 4) to 10(exp 9) M/atm for ethanol under upper tropospheric conditions (210-240 K, 40-80 wt. % H2S04). The multiple solvation pathways (protonation, enolization, etc.) available to these compounds in acidic aqueous environments will be discussed. Preliminary results from the interaction of acetaldehyde with solutions of formaldehyde in sulfuric acid will be presented as well. The physical and chemical processes that affect organic uptake by aqueous aerosols will be explored, with the aim of evaluating organic species not yet studied in low temperature aqueous sulfuric acid.

  17. Second organic aerosol formation from the ozonolysis of α-pinene in the presence of dry submicron ammonium sulfate aerosol

    Institute of Scientific and Technical Information of China (English)

    ZHAO Zhe; HAO Jiming; LI Junhua; WU Shan

    2008-01-01

    An indoor chamber facility is described for investigation of atmospheric aerosol chemistry. Two sets of α-pinene ozonolysisexperiments were conducted in the presence of dry ammonium sulfate seed particle: ozone limited experiments and α-pinene limitedexperiments. The concentration of gas phase and particle phase species was monitored continuously by on-line instruments andrecorded automatically by data sampling system. The evolution of size distribution was measured by a scanning mobility particlesizer (SMPS), and α-pinene consumed was measured using GC-FID. Secondary organic aerosol (SOA) produced for seed-free systemis 100% organic in content, resulting from a sufficient supersaturation of low volatility organics to produce homogeneous nucleationfollowed by condensation to the aerosol. Secondary organic aerosol produced in seeded system is a mixture of organic and inorganicconstituents, initially forms via condensation onto the inorganic particles, and subsequent growth occurs via absorption into the organicsurface coating the inorganic core. Although the formation process and the size distribution for seed-free system and seeded system isdifferent, the ultimate mass of SOA formed is equal, and SOA yield for the two system located in the same regression line when usingone-product model, suggesting that the presence of dry ammonium sulfate seed has no measurable effect on the total aerosol yield, and the dry seed particle acts solely as a site upon which organic deposition occurs.

  18. Effect of sulfate aerosol on tropospheric NOx and ozone budgets: Model simulations and TOPSE evidence

    Science.gov (United States)

    Tie, Xuexi; Emmons, Louisa; Horowitz, Larry; Brasseur, Guy; Ridley, Brian; Atlas, Elliot; Stround, Craig; Hess, Peter; Klonecki, Andrzej; Madronich, Sasha; Talbot, Robert; Dibb, Jack

    2003-02-01

    The distributions of NOx and O3 are analyzed during TOPSE (Tropospheric Ozone Production about the Spring Equinox). In this study these data are compared with the calculations of a global chemical/transport model (Model for OZone And Related chemical Tracers (MOZART)). Specifically, the effect that hydrolysis of N2O5 on sulfate aerosols has on tropospheric NOx and O3 budgets is studied. The results show that without this heterogeneous reaction, the model significantly overestimates NOx concentrations at high latitudes of the Northern Hemisphere (NH) in winter and spring in comparison to the observations during TOPSE; with this reaction, modeled NOx concentrations are close to the measured values. This comparison provides evidence that the hydrolysis of N2O5 on sulfate aerosol plays an important role in controlling the tropospheric NOx and O3 budgets. The calculated reduction of NOx attributed to this reaction is 80 to 90% in winter at high latitudes over North America. Because of the reduction of NOx, O3 concentrations are also decreased. The maximum O3 reduction occurs in spring although the maximum NOx reduction occurs in winter when photochemical O3 production is relatively low. The uncertainties related to uptake coefficient and aerosol loading in the model is analyzed. The analysis indicates that the changes in NOx due to these uncertainties are much smaller than the impact of hydrolysis of N2O5 on sulfate aerosol. The effect that hydrolysis of N2O5 on global NOx and O3 budgets are also assessed by the model. The results suggest that in the Northern Hemisphere, the average NOx budget decreases 50% due to this reaction in winter and 5% in summer. The average O3 budget is reduced by 8% in winter and 6% in summer. In the Southern Hemisphere (SH), the sulfate aerosol loading is significantly smaller than in the Northern Hemisphere. As a result, sulfate aerosol has little impact on NOx and O3 budgets of the Southern Hemisphere.

  19. Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NOx photooxidation

    Institute of Scientific and Technical Information of China (English)

    Biwu CHU; Jiming HAO; Junhua LI; Hideto TAKEKAWA; Kun WANG; Jingkun JIANG

    2013-01-01

    Aerosol phase reactions play a very important role on secondary organic aerosol (SOA) formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate (MnSO4) and zinc sulfate (ZnSO4), on the photochemical reactions of a toluene/NOx photooxidation system in a 2 m3 smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NOx conversion and the formation of ozone and SOA. MnSO4 and ZnSO4 seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO4 and ZnSO4 seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.

  20. Effects of the physical state of tropospheric ammonium-sulfate-nitrate particles on global aerosol direct radiative forcing

    Directory of Open Access Journals (Sweden)

    S. T. Martin

    2003-10-01

    Full Text Available The effect of aqueous versus crystalline sulfate-nitrate-ammonium tropospheric particles on global aerosol direct radiative forcing is assessed. A global three-dimensional chemical transport model predicts sulfate, nitrate, and ammonium aerosol mass. An aerosol thermodynamics model is called twice, once for the upper side (US and once for lower side (LS of the hysteresis loop of particle phase. On the LS, the sulfate mass budget is 40% solid ammonium sulfate, 12% letovicite, 11% ammonium bisulfate, and 37% aqueous. The LS nitrate mass budget is 26% solid ammonium nitrate, 7% aqueous, and 67% gas-phase nitric acid release due to increased volatility upon crystallization. The LS ammonium budget is 45% solid ammonium sulfate, 10% letovicite, 6% ammonium bisulfate, 4% ammonium nitrate, 7% ammonia release due to increased volatility, and 28% aqueous. LS aerosol water mass partitions as 22% effloresced to the gas-phase and 78% remaining as aerosol mass. The predicted US/LS global fields of aerosol mass are employed in a Mie scattering model to generate global US/LS aerosol optical properties, including scattering efficiency, single scattering albedo, and asymmetry parameter. Global annual average LS optical depth and mass scattering efficiency are, respectively, 0.023 and 10.7 m2  (g SO42−−1, which compare to US values of 0.030 and 13.9 m2 (g SO42−−1. Radiative transport is computed, first for a base case having no aerosol and then for the two global fields corresponding to the US and LS of the hysteresis loop. Regional, global, seasonal, and annual averages of top-of-the-atmosphere aerosol radiative forcing on the LS and US (FL and FU, respectively, in W m2− are calculated. Including both anthropogenic and natural emissions, we obtain global annual averages of FL = −0.750, FU = −0.930, and

  1. Characteristics of Anthropogenic Sulfate and Carbonaceous Aerosols over East Asia: Regional Modeling and Observation

    Institute of Scientific and Technical Information of China (English)

    Yan HUANG; William L. CHAMEIDES; Qian TAN; Robert E. DICKINSON

    2008-01-01

    The authors present spatial and temporal characteristics of anthropogenic sulfate and carbonaceous aerosols over East Asia using a 3-D coupled regional climate-chemistry-aerosol model, and compare the simulation with the limited aerosol observations over the region. The aerosol module consists of SO2, SO42-, hydrophobic and hydrophilic black carbon (BC) and organic carbon compounds (OC), including emission, advections, dry and wet deposition, and chemical production and conversion. The simulated patterns of SO2 are closely tied to its emission rate, with sharp gradients between the highly polluted regions and more rural areas. Chemical conversion (especially in the aqueous phase) and dry deposition remove 60% and 30% of the total SO2 emission, respectively. The SO42- shows less horizontal gradient and seasonality than SO2, with wet deposition (60%) and export (27%) being two major sinks. Carbonaceous aerosols are spatially smoother than sulfur species. The aging process transforms more than 80% of hydrophobic BC and OC to hydrophilic components, which are removed by wet deposition (60%) and export (30%). The simulated spatial and seasonal SO42-, BC and OC aerosol concentrations and total aerosol optical depth are generally consistent with the observations in rural areas over East Asia, with lower bias in simulated OC aerosols, likely due to the underestimation of anthropogenic OC emissions and missing treatment of secondary organic carbon. The results suggest that our model is a useful tool for characterizing the anthropogenic aerosol cycle and for assessing its potential climatic and environmental effects in future studies.

  2. Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China.

    Science.gov (United States)

    Han, Xiaokun; Guo, Qingjun; Liu, Congqiang; Fu, Pingqing; Strauss, Harald; Yang, Junxing; Hu, Jian; Wei, Lianfang; Ren, Hong; Peters, Marc; Wei, Rongfei; Tian, Liyan

    2016-07-20

    Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ(34)Ssulfate and δ(18)Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ(34)S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ(34)Ssulfate and δ(18)Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere.

  3. Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China

    Science.gov (United States)

    Han, Xiaokun; Guo, Qingjun; Liu, Congqiang; Fu, Pingqing; Strauss, Harald; Yang, Junxing; Hu, Jian; Wei, Lianfang; Ren, Hong; Peters, Marc; Wei, Rongfei; Tian, Liyan

    2016-07-01

    Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ34Ssulfate and δ18Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ34S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ34Ssulfate and δ18Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere.

  4. The impact of dust on sulfate aerosol, CN and CCN during an East Asian dust storm

    Science.gov (United States)

    Manktelow, P. T.; Carslaw, K. S.; Mann, G. W.; Spracklen, D. V.

    2010-01-01

    A global model of aerosol microphysics is used to simulate a large East Asian dust storm during the ACE-Asia experiment. We use the model together with size resolved measurements of aerosol number concentration and composition to examine how dust modified the production of sulfate aerosol and the particle size distribution in East Asian outflow. Simulated size distributions and mass concentrations of dust, sub- and super-micron sulfate agree well with observations from the C-130 aircraft. Modeled mass concentrations of fine sulfate (Dp1.0 μm) by more than an order of magnitude, but total sulfate concentrations increase by less than 2% because decreases in fine sulfate have a compensating effect. Our analysis shows that the sulfate associated with dust can be explained largely by the uptake of H2SO4 rather than reaction of SO2 on the dust surface, which we assume is suppressed once the particles are coated in sulfate. We suggest that many previous model investigations significantly overestimated SO2 oxidation on East Asian dust, possibly due to the neglect of surface saturation effects. We extend previous model experiments by examining how dust modified existing particle concentrations in Asian outflow. Total particle concentrations (condensation nuclei, CN) modeled in the dust-pollution plume are reduced by up to 20%, but we predict that dust led to less than 10% depletion in particles large enough to act as cloud condensation nuclei (CCN). Our analysis suggests that E. Asian dust storms have only a minor impact on sulfate particles present at climate-relevant sizes.

  5. Sensitivity of thermal infrared nadir instruments to the chemical and microphysical properties of UTLS secondary sulfate aerosols

    Science.gov (United States)

    Sellitto, P.; Legras, B.

    2016-01-01

    Monitoring upper-tropospheric-lower-stratospheric (UTLS) secondary sulfate aerosols and their chemical and microphysical properties from satellite nadir observations is crucial to better understand their formation and evolution processes and then to estimate their impact on UTLS chemistry, and on regional and global radiative balance. Here we present a study aimed at the evaluation of the sensitivity of thermal infrared (TIR) satellite nadir observations to the chemical composition and the size distribution of idealised UTLS sulfate aerosol layers. The extinction properties of sulfuric acid/water droplets, for different sulfuric acid mixing ratios and temperatures, are systematically analysed. The extinction coefficients are derived by means of a Mie code, using refractive indices taken from the GEISA (Gestion et Étude des Informations Spectroscopiques Atmosphériques: Management and Study of Spectroscopic Information) spectroscopic database and log-normal size distributions with different effective radii and number concentrations. IASI (Infrared Atmospheric Sounding Interferometer) pseudo-observations are generated using forward radiative transfer calculations performed with the 4A (Automatized Atmospheric Absorption Atlas) radiative transfer model, to estimate the impact of the extinction of idealised aerosol layers, at typical UTLS conditions, on the brightness temperature spectra observed by this satellite instrument. We found a marked and typical spectral signature of these aerosol layers between 700 and 1200 cm-1, due to the absorption bands of the sulfate and bisulfate ions and the undissociated sulfuric acid, with the main absorption peaks at 1170 and 905 cm-1. The dependence of the aerosol spectral signature to the sulfuric acid mixing ratio, and effective number concentration and radius, as well as the role of interfering parameters like the ozone, sulfur dioxide, carbon dioxide and ash absorption, and temperature and water vapour profile uncertainties

  6. Modeling the spectral optical properties of ammonium sulfate and biomass burning aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Grant, K.E.; Chuang, C.C.; Grossman, A.S.; Penner, J.E. [Michigan Univ., Ann Arbor, MI (United States)

    1997-09-01

    The importance of including the global and regional radiative effects of aerosols in climate models has increasingly been realized. Accurate modeling of solar radiative forcing due to aerosols from anthropogenic sulfate and biomass burning emissions requires adequate spectral resolution and treatment of spatial and temporal variability. The variation of aerosol spectral optical properties with local relative humidity and dry aerosol composition must be considered. Because the cost of directly including Mie calculations within a climate model is prohibitive, parameterizations from offline calculations must be used. Starting from a log-normal size distribution of dry ammonium sulfate, we developed optical properties for tropospheric sulfate aerosol at 15 relative humidities up to 99 percent. The resulting aerosol size distributions were then used to calculate bulk optical properties at wavelengths between 0.175 {micro}m and 4 {micro}m. Finally, functional fits of optical properties were made for each of 12 wavelength bands as a function of relative humidity. Significant variations in optical properties occurred across the total solar spectrum. Relative increases in specific extinction and asymmetry factor with increasing relative humidity became larger at longer wavelengths. Significant variation in single-scattering albedo was found only in the longest near-IR band. This is also the band with the lowest albedo. A similar treatment was done for aerosols from biomass burning. In this case, size distributions were taken as having two carbonaceous size modes and a larger dust mode. The two carbonaceous modes were considered to be humidity dependent. Equilibrium size distributions and compositions were calculated for 15 relative humidities and five black carbon fractions. Mie calculations and Chandrasekhar averages of optical properties were done for each of the resulting 75 cases. Finally, fits were made for each of 12 spectral bands as functions of relative humidity

  7. Evidence for surface nucleation: efflorescence of ammonium sulfate and coated ammonium sulfate aerosol particles

    Science.gov (United States)

    Ciobanu, V. Gabriela; Marcolli, Claudia; Krieger, Ulrich K.; Zuend, Andreas; Peter, Thomas

    2010-05-01

    Aerosol particles are ubiquitous in the atmosphere and can undergo different phase transitions, such as deliquescence and efflorescence. Using optical microscopy, we investigated the efflorescence of ammonium sulfate (AS) in supersaturated AS and 1:1 and 8:1 (by weight) poly(ethylene glycol)-400 (PEG-400)/AS particles, which were deposited as droplets with diameters in the 16 - 35 μm range on a hydrophobically coated slide. The PEG-400/AS particles that are exposed to decreasing relative humidity (RH) exhibit a liquid-liquid phase separation below 90 % RH with the PEG-400 phase surrounding the aqueous AS inner phase (Marcolli and Krieger, 2006; Ciobanu et al., 2009). Pure AS particles effloresced in the RH range from 36.3 to 43.7 % RH, in agreement with literature data (31 - 48 % RH). In contrast, 1:1 PEG-400/AS particles with diameters of the AS phase from 7.2 - 19.2 μm effloresced between 26.8 - 33.9 % RH and 8:1 PEG-400/AS particles with diameters of the AS phase from 1.8 - 7.3 μm between 24.3 - 29.3 % RH. Such low efflorescence relative humidity (ERH) values have never been reached before for AS particles of this size range. We show that neither a potential inhibition of water evaporation via anomalously slow diffusion through the PEG coating, nor the presence of low amounts of PEG-400 in the AS phase, nor different timescales between various experimental techniques could possibly explain the low AS ERH values of PEG-400/AS particles in our setup. High-speed photography of the efflorescence process allowed to monitor the proceeding of the AS crystallization fronts within the particles with millisecond time resolution. The nucleation locations were deduced based on the initial crystals growth locations. Statistical analysis of 31 and 19 efflorescence events for pure AS and 1:1 PEG-400/AS particles, respectively, identified the air/droplet/substrate contact line and the air/droplet interface as preferred nucleation locations in the case of pure AS particles

  8. Solid/liquid phase diagram of the ammonium sulfate/succinic acid/water system.

    Science.gov (United States)

    Pearson, Christian S; Beyer, Keith D

    2015-05-14

    We have studied the low-temperature phase diagram and water activities of the ammonium sulfate/succinic acid/water system using differential scanning calorimetry and infrared spectroscopy of thin films. Using the results from our experiments, we have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/succinic acid phase boundary as well as the ternary eutectic composition and temperature. We also compared our results to the predictions of the extended AIM aerosol thermodynamics model (E-AIM) and found good agreement for the ice melting points in the ice primary phase field of this system; however, differences were found with respect to succinic acid solubility temperatures. We also compared the results of this study with those of previous studies that we have published on ammonium sulfate/dicarboxylic acid/water systems.

  9. Predictive mapping of the acidifying potential for acid sulfate soils

    DEFF Research Database (Denmark)

    Boman, A; Beucher, Amélie; Mattbäck, S

    Developing methods for the predictive mapping of the potential environmental impact from acid sulfate soils is important because recent studies (e.g. Mattbäck et al., under revision) have shown that the environmental hazards (e.g. leaching of acidity) related to acid sulfate soils vary depending...... on their texture (clay, silt, sand etc.). Moreover, acidity correlates, not only with the sulfur content, but also with the electrical conductivity (EC) measured after incubation. Electromagnetic induction (EMI) data collected from an EM38 proximal sensor also enabled the detailed mapping of acid sulfate soils...... over a field (Huang et al., 2014).This study aims at assessing the use of EMI data for the predictive mapping of the acidifying potential in an acid sulfate soil area in western Finland. Different supervised classification modelling techniques, such as Artificial Neural Networks (Beucher et al., 2015...

  10. Biological functions of iduronic acid in chondroitin/dermatan sulfate.

    Science.gov (United States)

    Thelin, Martin A; Bartolini, Barbara; Axelsson, Jakob; Gustafsson, Renata; Tykesson, Emil; Pera, Edgar; Oldberg, Åke; Maccarana, Marco; Malmstrom, Anders

    2013-05-01

    The presence of iduronic acid in chondroitin/dermatan sulfate changes the properties of the polysaccharides because it generates a more flexible chain with increased binding potentials. Iduronic acid in chondroitin/dermatan sulfate influences multiple cellular properties, such as migration, proliferation, differentiation, angiogenesis and the regulation of cytokine/growth factor activities. Under pathological conditions such as wound healing, inflammation and cancer, iduronic acid has diverse regulatory functions. Iduronic acid is formed by two epimerases (i.e. dermatan sulfate epimerase 1 and 2) that have different tissue distribution and properties. The role of iduronic acid in chondroitin/dermatan sulfate is highlighted by the vast changes in connective tissue features in patients with a new type of Ehler-Danlos syndrome: adducted thumb-clubfoot syndrome. Future research aims to understand the roles of the two epimerases and their interplay with the sulfotransferases involved in chondroitin sulfate/dermatan sulfate biosynthesis. Furthermore, a better definition of chondroitin/dermatan sulfate functions using different knockout models is needed. In this review, we focus on the two enzymes responsible for iduronic acid formation, as well as the role of iduronic acid in health and disease.

  11. Role of sucrose in the heterogeneous uptake of dimethylamine by ammonium sulfate aerosol particles

    Science.gov (United States)

    Chu, Y.; Chan, C. K.

    2016-12-01

    Alkyl amines are important alkaline gases besides ammonia in the atmosphere and widely detected in both gas and particle phases. Heterogeneous uptake by pre-existing particles containing acids as well as ammonium salts is one of the major pathways of alkyl amines partitioning into aerosols. Recently, phase state of ammonium salt particles has been revealed to largely affect the degree of alkyl amines uptake. Using an electrodynamic balance coupled with Raman spectroscopy, we extend the study by investigating the alkyl amine uptake by ammonium sulfate (AS) - sucrose mixed particles, since ambient aerosols usually consist of a mixed phase of organics and inorganics. Sucrose is a surrogate of hydrophilic viscous organics that can alter the phase of AS at low relative humidity (RH) and dimethylamine (DMA) is selected for its abundance amongst alkyl amine compounds. DMA uptake occurred effectively at not only 70% RH but also RH as low as 10%, significantly below the AS crystallization point. The net uptake coefficient decreased as RH decreased for fixed initial AS - sucrose particle compositions. Interestingly, it followed a first increasing then decreasing trend as sucrose molar fraction increased from 0 to 0.5, at RH below 30%. Sucrose, albeit inert to DMA vapor, indirectly affected the interaction between DMA and AS - sucrose particles. On one hand, it absorbed water at low RH and delayed the efflorescence of AS to promote DMA uptake. On the other hand, the particle became more viscous with higher sucrose concentration and exhibited an effective mass transport barrier. Hence, the uptake of alkyl amines may occur slowly once ammonium salts are mixed with viscous organics, such as those secondary organic materials formed via the oxidation of biogenic volatile organic compounds, in the particle phase. Acknowledgment This work is supported by Research Grants Council (RGC) of Hong Kong Special Administrative Region, China (GRF 16300214). The grant from Hong Kong RGC Ph

  12. Fatty Acids as Surfactants on Aerosol Particles

    Science.gov (United States)

    Tervahattu, H.; Juhanoja, J.; Niemi, J.

    2003-12-01

    Fatty acids (n-alcanoic acids) are common compounds in numerous anthropogenic and natural emissions. According to Rogge et al. (1993), catalyst-equipped automobiles emitted more than 600 μg km-1 of fatty acids which was over 50% of all identified organics in fine aerosol emissions. Coal burning produces fatty acids ranging from about 1700 mg kg-1 for bituminous coal to over 10000 mg kg-1 for lignite (Oros and Simoneit, 2000). Similarly, biomass burning is an important source for aerosol fatty acids. They are the major identified compound group in deciduous tree smoke, their total emission factor being measured as 1589 mg kg-1 which was 56% of all identified organic compounds (Oros and Simoneit, 2001a). Large amounts of fatty acid are also emitted from burning of conifer trees and grass (Oros and Simoneit, 2001a; Simoneit, 2002). Fatty acids have been reported to be major constituents of marine aerosols in many investigations (Barger and Garrett, 1976; Gagosian et. al, 1981; Sicre et al., 1990; Stephanou, 1992). It has been suggested that as the marine aerosol particles form, they acquire a coating of organic surfactants (Blanchard, 1964; Gill et al., 1983; Middlebrook et al., 1998; Ellison et al., 1999). Amphiphilic molecules, including lipids, can be assembled as monomolecular layers at air/water interfaces as well as transported to a solid support. Recently, we could show by time-of-flight secondary ion mass spectrometry that fatty acids are important ingredients of the outermost surface layer of the sea-salt aerosol particles (Tervahattu et al., 2002). In their TOF-SIMS studies on the surface composition of atmospheric aerosols, Peterson and Tyler (2002) found fatty acids on the surface of Montana forest fire particles. In this work we have studied by TOF-SIMS the surface chemical composition of aerosol particles emitted from field fires in the Baltic and other East European countries and transported to Finland as well as aerosol particles transported from

  13. Evaluating Ammonium, Nitrate and Sulfate Aerosols in 3-Dimensions

    Science.gov (United States)

    Mezuman, Keren; Bauer, Susanne E.; Tsigaridis, Kostas

    2015-01-01

    The effect aerosols have on climate and air quality is a func-on of their chemical composi-on, concentra-on and spa-al distribu-on. These parameters are controlled by emissions, heterogeneous and homogeneous chemistry, where thermodynamics plays a key role, transport, which includes stratospheric-­- tropospheric exchange, and deposi-onal sinks. In this work we demonstrate the effect of some of these processes on the SO4-NH4­-NO3 system using the GISS ModelE2 Global Circula-on Model (GCM).

  14. NUMERICAL SIMULATION WITH A COMPREHENSIVE CHEMICAL TRANSPORT MODEL OF NITRATE, SULFATE, AND AMMONIUM AEROSOL DISTRIBUTIONS OVER EAST ASIA

    Institute of Scientific and Technical Information of China (English)

    Meigen Zhang

    2005-01-01

    The transport and chemical production processes of nitrate, sulfate, and ammonium aerosols over East Asia were investigated by use of the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system coupled with the Regional Atmospheric Modeling System (RAMS). For the evaluation of the model's ability in depicting their3-dimensional concentration distributions and temporal variations, modeled concentrations of nitrate, sulfate, and ammonium aerosols are compared with the observations obtained at a ground station in Japan in March 2001 and onboard of an aircraft DC-8 on 18 and 21 March 2001 during the Transport and Chemical Evolution over the Pacific (TRACE-P)field campaign. Comparison shows that simulated values of nitrate, sulfate, and ammonium aerosols are generally in good agreement with their observed data, and the model captures most important observed features, and reproduces temporal and spatial variations of nitrate, sulfate, and ammonium aerosol concentrations reasonably well, e.g., the timing and locations of the concentration spikes of nitrate, sulfate, and ammonium aerosols are well reproduced, but large discrepancies between observed and simulated values are also clearly seen at some points and some times due to the coarse grid resolution and uncertainties of the emissions used in this study. This comparison results indicate that CMAQ is able to simulate the distributions of nitrate, sulfate, and ammonium aerosols and their related species in the troposphere over East Asia reasonably well.

  15. Effects of sulfate aerosol forcing on East Asian summer monsoon for 1985-2010

    Science.gov (United States)

    Kim, Minjoong J.; Yeh, Sang-Wook; Park, Rokjin J.

    2016-02-01

    We examine the effect of anthropogenic aerosol forcing on the East Asian summer monsoon (EASM) using the Community Atmosphere Model version 5.1.1. One control and two sensitivity model experiments were conducted in order to diagnose the separate roles played by sea surface temperature (SST) variations and anthropogenic sulfate aerosol forcing changes in East Asia. We find that the SST variation has been a major driver for the observed weakening of the EASM, whereas the effect of the anthropogenic aerosol forcing has been opposite and has slightly intensified the EASM over the recent decades. The reinforcement of the EASM results from radiative cooling by the sulfate aerosol forcing, which decelerates the jet stream around the jet's exit region. Subsequently, the secondary circulation induced by such a change in the jet stream leads to the increase in precipitation around 18-23°N. This result indicates that the increase in anthropogenic emissions over East Asia may play a role in compensating for the weakening of the EASM caused by the SST forcing.

  16. Internally mixed soot, sulfates, and organic matter in aerosol particles from Mexico City

    Directory of Open Access Journals (Sweden)

    K. Adachi

    2008-11-01

    Full Text Available Soot particles, which are aggregated carbonaceous spherules with graphitic structures, are major aerosol constituents that result from burning of fossil fuel, biofuel, and biomass. Their properties commonly change through reaction with other particles or gases, resulting in complex internal mixtures. Using a transmission electron microscope (TEM for both imaging and chemical analysis, we measured ~8000 particles (25 samples with aerodynamic diameters from 0.05 to 0.3 μm that were collected in March 2006 from aircraft over Mexico City (MC and adjacent areas. Most particles are coated, consist of aggregates, or both. For example, almost all analyzed particles contain S and 70% also contain K, suggesting coagulation and condensation of sulfates and particles derived from biomass and biofuel burning. In the MC plumes, over half of all particles contained soot coated by organic matter and sulfates. The median value of the soot volume fraction in such coated particles is about 15%. In contrast to the assumptions used in many climate models, the soot particles did not become compact even when coated. Moreover, about 80% by volume of the particles consisting of organic matter with sulfate also contained soot, indicating the important role of soot in the formation of secondary aerosol particles. Coatings on soot particles can amplify their light absorption, and coagulation with sulfates changes their hygroscopic properties, resulting in shorter lifetimes. Through changes in their optical and hygroscopic properties, internally mixed soot particles have a greater effect on the regional climate of MC than uncoated soot particles.

  17. Comparative potency of inhaled acidic sulfates: speciation and the role of hydrogen ion.

    Science.gov (United States)

    Schlesinger, R B; Chen, L C; Finkelstein, I; Zelikoff, J T

    1990-08-01

    Inhaled acidic sulfate aerosols affect various aspects of lung function, presumably by delivery of hydrogen ion (H+) to target sites. Recent evidence suggests that the relationship between response and H+ content of the exposure atmosphere may depend upon the specific sulfate species with which the H+ is associated. This study examined comparatively the effects of exposure to the two main ambient acidic sulfates, sulfuric acid (H2SO4) and ammonium bisulfate (NH4HSO4), using the phagocytic activity of alveolar macrophages as the endpoint. Rabbits were exposed to 250-2000 micrograms/m3 H2SO4 (as SO4(-2)) and 500-4000 micrograms/m3 NH4HSO4 (as SO4(-2)) for 1 hr/day for 5 days; bronchopulmonary lavage was then performed for recovery of free lung cells. Phagocytosis, measured by uptake of opsonized latex spheres in vitro, was altered by exposure to H2SO4 at concentrations greater than or equal to 500 micrograms/m3 and to NH4HSO4 at greater than or equal to 2000 micrograms/m3. Assessment of results in terms of the calculated hydrogen ion concentration in the exposure atmosphere showed that identical levels of H+ produced different degrees of response depending upon whether exposure was to H2SO4 or NH4HSO4. On the other hand, macrophages incubated in acidic environments in vitro responded similarly regardless of whether H2SO4 or NH4HSO4 was used to adjust the pH. Possible reasons for the difference in response observed in vivo and in vitro are discussed. Speciation of ambient acidic sulfate aerosols may be needed in atmospheric monitoring so as to assess the presence of H+ posing the greatest biologic hazard following inhalation exposure.

  18. Characteristics of Phosphorus in Some Eastern Australian Acid Sulfate Soils

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Forty-five acid sulfate topsoil samples (depth < 0.5 m) from 15 soil cores were collected from 11 locations along the New South Wales coast, Australia. There was an overall trend for the concentration of the HC1extractable P to increase along with increasing amounts of organic C and the HCl-extractable trivalent metals in the topsoils of some less-disturbed acid sulfate soils (pH <4.5). This suggests that inorganic P in these soils probably accumulated via biological cycling and was retained by complexation with trivalent metals or their oxides and hydroxides. While there was no clear correlation between pH and the water-extractable P, the concentration of the water-extractable P tended to increase with increasing amounts of the HCl-extractable P. This disagrees with some established models which suggest that the concentration of solution P in acid soils is independent of total P and decreases with increasing acidity. The high concentration of sulfate present in acid sulfate soils appeared to affect the chemical behavior of P in these soil systems. Comparison was made between a less disturbed wetland acid sulfate soil and a more intensively disturbed sugarcane acid sulfate soil.The results show that reclamation of wetland acid sulfate soils for sugarcane production caused a significant decrease in the HCl-extractable P in the topsoil layer as a result of the reduced bio-cycling of phosphorus following sugarcane farming. Simulation experiment shows that addition of hydrated lime had no effects on the immobilization of retained P in an acid sulfate soil sample within a pH range 3.5~4.6. When the pH was raised to above 4.6, soluble P in the soil extracts had a tendency to increase with increasing pH until the 15th extraction (pH 5.13). This, in combination with the poor pH-soluble P relationship observed from the less-disturbed acid sulfate soils, suggests that soluble P was not clearly pH-dependent in acid sulfate soils with pH < 4.5.

  19. Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol.

    Science.gov (United States)

    Huang, Mingqiang; Zhang, Jiahui; Cai, Shunyou; Liao, Yingmin; Zhao, Weixiong; Hu, Changjin; Gu, Xuejun; Fang, Li; Zhang, Weijun

    2016-09-01

    Aging of secondary organic aerosol (SOA) particles formed from OH- initiated oxidation of ethylbenzene in the presence of high mass (100-300μg/m(3)) concentrations of (NH4)2SO4 seed aerosol was investigated in a home-made smog chamber in this study. The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with a Fuzzy C-Means (FCM) clustering algorithm. Experimental results showed that nitrophenol, ethyl-nitrophenol, 2,4-dinitrophenol, methyl glyoxylic acid, 5-ethyl-6-oxo-2,4-hexadienoic acid, 2-ethyl-2,4-hexadiendioic acid, 2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid, 1H-imidazole, hydrated N-glyoxal substituted 1H-imidazole, hydrated glyoxal dimer substituted imidazole, 1H-imidazole-2-carbaldehyde, N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight (HMW) components were the predominant products in the aged particles. Compared to the previous aromatic SOA aging studies, imidazole compounds, which can absorb solar radiation effectively, were newly detected in aged ethylbenzene SOA in the presence of high concentrations of (NH4)2SO4 seed aerosol. These findings provide new information for discussing aromatic SOA aging mechanisms.

  20. Assessment of the first indirect radiative effect of ammonium-sulfate-nitrate aerosols in East Asia

    Science.gov (United States)

    Han, Xiao; Zhang, Meigen; Skorokhod, Andrei

    2016-09-01

    A physically based cloud nucleation parameterization was introduced into an optical properties/radiative transfer module incorporated with the off-line air quality modeling system Regional Atmospheric Modeling System (RAMS)-Models-3 Community Multi Scale Air Quality (CMAQ) to investigate the distribution features of the first indirect radiative effects of sulfate, nitrate, and ammonium-sulfate-nitrate (ASN) over East Asia for the years of 2005, 2010, and 2013. The relationship between aerosol particles and cloud droplet number concentration could be properly described by this parameterization because the simulated cloud fraction and cloud liquid water path were generally reliable compared with Moderate Resolution Imaging Spectroradiometer (MODIS) retrieved data. Simulation results showed that the strong effect of indirect forcing was mainly concentrated in Southeast China, the East China Sea, the Yellow Sea, and the Sea of Japan. The highest indirect radiative forcing of ASN reached -3.47 W m-2 over Southeast China and was obviously larger than the global mean of the indirect forcing of all anthropogenic aerosols. In addition, sulfate provided about half of the contribution to the ASN indirect forcing effect. However, the effect caused by nitrate was weak because the mass burden of nitrate was very low during summer, whereas the cloud fraction was the highest. The analysis indicated that even though the interannual variation of indirect forcing magnitude generally followed the trend of aerosol mass burden from 2005 to 2013, the cloud fraction was an important factor that determined the distribution pattern of indirect forcing. The heaviest aerosol loading in North China did not cause a strong radiative effect because of the low cloud fraction over this region.

  1. Evaluating the potential influence of inter-continental transport of sulfate aerosols on air quality

    Science.gov (United States)

    Mauzerall, D. L.; Liu, J.

    2007-12-01

    In this study, we compare the potential influence of inter-continental transport of sulfate aerosols on the air quality of continental regions. We use a global chemical transport model, Model of Ozone and Related Tracers, version 2 (MOZART-2), to quantify the source-receptor relationships of inter-continental transport of sulfate aerosols among ten regions in 2000. In order to compare the importance of foreign emissions relative to domestic emissions and estimate the effect of future changes in emissions on human exposure, we define an "influence potential" (IP). The IP quantifies the human exposure that occurs in a receptor region as a result of a unit of SO2 emissions from a source region. We find that due to the non-linear nature of sulfate production, regions with low SO2 emissions usually have large domestic IP, and vice versa. An exception is East Asia (EA), which has both high SO2 emissions and relatively large domestic IP, mostly caused by the spatial coincidence of emissions and population. We find that intercontinental IPs are usually less than domestic IPs by 1-3 orders of magnitude. SO2 emissions from the Middle East (ME) and Europe (EU) have the largest potential to influence populations in surrounding regions. By comparing the IP ratios (IPR) between foreign and domestic SO2 emissions, we find that the IPR values range from 0.00001 to 0.16 and change with season. Therefore, if reducing human exposure to sulfate aerosols is the objective, all regions should first focus on reducing domestic SO2 emissions. In addition, we find that relatively high IPR values exist among the EU, ME, the former Soviet Union (FSU) and African (AF) regions. Therefore, based on the IP and IPR values, we conclude that a regional agreement among EA countries, and an inter-regional agreement among EU, ME, FSU and north AF regions to control sulfur emissions would benefit public health in these regions.

  2. Potential influence of inter-continental transport of sulfate aerosols on air quality

    Science.gov (United States)

    Liu, Junfeng; Mauzerall, Denise L.

    2007-10-01

    In this study, we compare the potential influence of inter-continental transport of sulfate aerosols on the air quality of (different) continental regions. We use a global chemical transport model, Model of Ozone and Related Tracers, version 2 (MOZART-2), to quantify the source receptor relationships of inter-continental transport of sulfate aerosols among ten regions in 2000. In order to compare the importance of foreign with domestic emissions and to estimate the effect of future changes in emissions on human exposure, we define an 'influence potential' (IP). The IP quantifies the human exposure that occurs in a receptor region as a result of a unit of SO2 emissions from a source region. We find that due to the non-linear nature of sulfate production, regions with low SO2 emissions usually have large domestic IP, and vice versa. An exception is East Asia (EA), which has both high SO2 emissions and relatively large domestic IP, mostly caused by the spatial coincidence of emissions and population. We find that inter-continental IPs are usually less than domestic IPs by 1 3 orders of magnitude. SO2 emissions from the Middle East (ME) and Europe (EU) have the largest potential to influence populations in surrounding regions. By comparing the IP ratios (IPR) between foreign and domestic SO2 emissions, we find that the IPR values range from 0.000 01 to 0.16 and change with season. Therefore, if reducing human exposure to sulfate aerosols is the objective, all regions should first focus on reducing domestic SO2 emissions. In addition, we find that relatively high IPR values exist among the EU, ME, the former Soviet Union (FSU) and African (AF) regions. Therefore, on the basis of the IP and IPR values, we conclude that a regional agreement among EA countries, and an inter-regional agreement among EU, ME, FSU and (north) AF regions to control sulfur emissions could benefit public health in these regions.

  3. Effects of ammonium sulfate aerosols on vegetation—II. Mode of entry and responses of vegetation

    Science.gov (United States)

    Gmur, Nicholas F.; Evans, Lance S.; Cunningham, Elizabeth A.

    These experiments were designed to provide information on the rates of aerosol deposition, mode of entry, and effects of deposition of submicrometer ammonium sulfate aerosols on foliage of Phaseolus vulgaris L. A deposition velocity of 3.2 × 10 3cms-1 was constant during 3-week exposures of plants to aerosol concentrations of 26mg m -3 (i.e. about two orders of magnitude above ambient episode concentrations). Mean deposition rate on foliage was 4.1 × 10 -11 μg cm -2s -1. Visible injury symptoms included leaf chlorosis, necrosis and loss of turgor. Chlorosis was most frequent near leaf margins causing epinasty and near major veins. Internal injury occurred initially in spongy mesophyll cells. Eventually abaxial epidermal and palisade parenchyma cells were injured. These results suggest that submicrometer aerosols enter abaxial stomata and affect more internal cells before affecting leaf surface cells. Exposure to aerosols decreased both abaxial and adaxial leaf resistances markedly. Although visible injury to foliage occurred, no changes in dry mass of roots and shoots or leaf area occurred. These results suggest that for the plant developmental stage studied, while leaf resistances decreased and cellular injury occurred in foliage, these factors were not significantly related to plant growth and development.

  4. Effects of ammonium sulfate aerosols on vegetation--II. Mode of entry and responses of vegetation

    Energy Technology Data Exchange (ETDEWEB)

    Gmur, N.F. (Brookhaven National Lab., Upton, NY); Evans, L.S.; Cunningham, E.A.

    1983-01-01

    These experiments were designed to provide information on the rates of aerosol deposition, mode of entry, and effects of deposition of submicrometer ammonium sulfate aerosols on foliage of Phaseolus vulgaris L. A deposition velocity of 3.2 x 10/sup -3/ cm s/sup -1/ was constant during 3-week exposures of plants to aerosol concentrations of 26mg m/sup -3/ (i.e., about two orders of magnitude above ambient episode concentrations). Mean deposition rate on foliage was 4.1 x 10/sup -11/ ..mu..g cm/sup -2/ s/sup -1/. Visible injury symptoms included leaf chlorosis, necrosis, and loss of turgor. Chlorosis was most frequent near leaf margins causing epinasty and near major veins. Internal injury occurred initially in spongy mesophyll cells. Eventually abaxial epidermal and palisade parenchyma cells were injured. These results suggest that submicrometer aerosols enter abaxial stomata and affect more internal cells before affecting leaf surface cells. Exposure to aerosols decreased both abaxial and adaxial leaf resistances markedly. Although visible injury to foliage occurred, no change in dry mass of roots and shoots or leaf area occurred. These results suggest that for the plant developmental stage studied, while leaf resistances decreased and cellular injury occurred in foliage, these factors were not significantly related to plant growth and development.

  5. Remediation of Acid Mine Drainage with Sulfate Reducing Bacteria

    Science.gov (United States)

    Hauri, James F.; Schaider, Laurel A.

    2009-01-01

    Sulfate reducing bacteria have been shown to be effective at treating acid mine drainage through sulfide production and subsequent precipitation of metal sulfides. In this laboratory experiment for undergraduate environmental chemistry courses, students design and implement a set of bioreactors to remediate acid mine drainage and explain observed…

  6. Remediation of Acid Mine Drainage with Sulfate Reducing Bacteria

    Science.gov (United States)

    Hauri, James F.; Schaider, Laurel A.

    2009-01-01

    Sulfate reducing bacteria have been shown to be effective at treating acid mine drainage through sulfide production and subsequent precipitation of metal sulfides. In this laboratory experiment for undergraduate environmental chemistry courses, students design and implement a set of bioreactors to remediate acid mine drainage and explain observed…

  7. Sulfated phenolic acids from Dasycladales siphonous green algae.

    Science.gov (United States)

    Kurth, Caroline; Welling, Matthew; Pohnert, Georg

    2015-09-01

    Sulfated aromatic acids play a central role as mediators of chemical interactions and physiological processes in marine algae and seagrass. Among others, Dasycladus vermicularis (Scopoli) Krasser 1898 uses a sulfated hydroxylated coumarin derivative as storage metabolite for a protein cross linker that can be activated upon mechanical disruption of the alga. We introduce a comprehensive monitoring technique for sulfated metabolites based on fragmentation patterns in liquid chromatography/mass spectrometry and applied it to Dasycladales. This allowed the identification of two new aromatic sulfate esters 4-(sulfooxy)phenylacetic acid and 4-(sulfooxy)benzoic acid. The two metabolites were synthesized to prove the mass spectrometry-based structure elucidation in co-injections. We show that both metabolites are transformed to the corresponding desulfated phenols by sulfatases of bacteria. In biofouling experiments with Escherichia coli and Vibrio natriegens the desulfated forms were more active than the sulfated ones. Sulfatation might thus represent a measure of detoxification that enables the algae to store inactive forms of metabolites that are activated by settling organisms and then act as defense. Copyright © 2015. Published by Elsevier Ltd.

  8. Composition and hygroscopicity of aerosol particles at Mt. Lu in South China: Implications for acid precipitation

    Science.gov (United States)

    Li, Weijun; Chi, Jianwei; Shi, Zongbo; Wang, Xinfeng; Chen, Bin; Wang, Yan; Li, Tao; Chen, Jianmin; Zhang, Daizhou; Wang, Zifa; Shi, Chune; Liu, Liangke; Wang, Wenxing

    2014-09-01

    Physicochemical properties of aerosol particles were studied at Mt. Lu, an elevated site (115°59‧E, 29°35‧N, 1165 m) within the acid precipitation area. Northeast winds transport copious amounts of air pollutants and water vapor from the Yangtze River Delta into this acid precipitation area. NH4+ and SO42- are the dominant ions in PM2.5 and determine aerosol acidity. Individual particle analysis shows abundant S-rich and metals (i.e. Fe-, Zn-, Mn-, and Pb-rich) particles. Unlike aerosol particles in North China and urban areas, there are little soot and mineral particles at Mt. Lu. Lack of mineral particles contributed to the higher acidity in precipitation in the research area. Nano-sized spherical metal particles were observed to be embedded in 37% of S-rich particles. These metal particles were likely originated from heavy industries and fired-power plants. Hygroscopic experiments show that most particles start to deliquesce at 73-76% but organic coating lowers the particle deliquescence relative humidity (DRH) to 63-73%. The DRHs of these aerosol particles are clearly smaller than that of pure ammonium sulfate particles which is 80%. Since RH in ambient air was relatively high, ranging from 65% to 85% during our study period, most particles at our sampling site were in liquid phase. Our results suggest that liquid phase reactions in aerosol particles may contribute to SO2 to sulfuric acid conversion in the acid precipitation area.

  9. Analytical Methods for Environmental Risk Assessment of Acid Sulfate Soils: A Review

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Assessment of acid sulfate soil risk is an important step for acid sulfate soil management and its reliability depends very much on the suitability and accuracy of various analytical methods for estimating sulfide-derived potential acidity, actual acidity and acid-neutralizing capacity in acid sulfate soils. This paper critically reviews various analytical methods that are currently used for determination of the above parameters, as well as their implications for environmental risk assessment of acid sulfate soils.

  10. Organic acids in continental background aerosols

    Science.gov (United States)

    Limbeck, Andreas; Puxbaum, Hans

    With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m -3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.

  11. Acidity-Reactivity Relationships in Catalytic Esterification over Ammonium Sulfate-Derived Sulfated Zirconia

    Directory of Open Access Journals (Sweden)

    Abdallah I. M. Rabee

    2017-07-01

    Full Text Available New insight was gained into the acidity-reactivity relationships of sulfated zirconia (SZ catalysts prepared via (NH42SO4 impregnation of Zr(OH4 for propanoic acid esterification with methanol. A family of systematically related SZs was characterized by bulk and surface analyses including XRD, XPS, TGA-MS, N2 porosimetry, temperature-programmed propylamine decomposition, and FTIR of adsorbed pyridine, as well as methylbutynol (MBOH as a reactive probe molecule. Increasing surface sulfation induces a transition from amphoteric character for the parent zirconia and low S loadings <1.7 wt %, evidenced by MBOH conversion to 3-hydroxy-3-methyl-2-butanone, methylbutyne and acetone, with higher S loadings resulting in strong Brønsted-Lewis acid pairs upon completion of the sulfate monolayer, which favored MBOH conversion to prenal. Catalytic activity for propanoic acid esterification directly correlated with acid strength determined from propylamine decomposition, coincident with the formation of Brønsted-Lewis acid pairs identified by MBOH reactive titration. Monodispersed bisulfate species are likely responsible for superacidity at intermediate sulfur loadings.

  12. ELECTRON DETACHMENT DISSOCIATION OF SYNTHETIC HEPARAN SULFATE GLYCOSAMINOGLYCAN TETRASACCHARIDES VARYING IN DEGREE OF SULFATION AND HEXURONIC ACID STEREOCHEMISTRY.

    Science.gov (United States)

    Leach, Franklin E; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I Jonathan

    2012-12-15

    Glycosaminoglycan (GAG) carbohydrates provide a challenging analytical target for structural determination due to their polydisperse nature, non-template biosynthesis, and labile sulfate modifications. The resultant structures, although heterogeneous, contain domains which indicate a sulfation pattern or code that correlates to specific function. Mass spectrometry, in particular electron detachment dissociation Fourier transform ion cyclotron resonance (EDD FT-ICR MS), provides a highly sensitive platform for GAG structural analysis by providing cross-ring cleavages for sulfation location and product ions specific to hexuronic acid stereochemistry. To investigate the effect of sulfation pattern and variations in stereochemistry on EDD spectra, a series of synthetic heparan sulfate (HS) tetrasaccharides are examined. Whereas previous studies have focused on lowly sulfated compounds (0.5-1 sulfate groups per disaccharide), the current work extends the application of EDD to more highly sulfated tetrasaccharides (1-2 sulfate groups per disaccharide) and presents the first EDD of a tetrasaccharide containing a sulfated hexuronic acid. For these more highly sulfated HS oligomers, alternative strategies are shown to be effective for extracting full structural details. These strategies inlcude sodium cation replacement of protons, for determining the sites of sulfation, and desulfation of the oligosaccharides for the generation of product ions for assigning uronic acid stereochemistry.

  13. Role of soot particles and NO/sub x/ in the oxidation of SO/sub 2/ in aqueous solution: kinetics, mechanism, and impact on sulfate-aerosol formation

    Energy Technology Data Exchange (ETDEWEB)

    Chang, S.G.; Brodzinsky, R.; Oblath, S.; Markowitz, S.; Toossi, R.; Novakov, T.

    1980-11-01

    Two previously unrecognized processes were identified which could play an important role in terms of acid rain and sulfate aerosol formation: (1) the oxidation of SO/sub 2/ in water droplets containing soot particles, and (2) the oxidation of SO/sub 2/ by NO/sub x/ in water droplets. 6 figures, 3 tables.

  14. THE ROLE OF SOOT PARTICLES AND NO{sub x} IN THE OXIDATION OF SO{sub 2} IN AQUEOUS SOLUTION: KINETICS, MECHANISM, AND IMPACT ON SULFATE AEROSOL FORMATION

    Energy Technology Data Exchange (ETDEWEB)

    Chang, S.G.; Brodzinsky, R.; Oblath, S.; Markowitz, S.; Toossi, R.; Novakov, T.

    1980-11-01

    We have identified two previously unrecognized processes which could play an important role in terms of acid rain and sulfate aerosol formation: 1) the oxidation of SO{sub 2} in water droplets containing soot particles, and 2) the oxidation of SO{sub 2} by NO{sub x} in water droplets. The results of our investigation on these two systems are outlined.

  15. Air pollution and asthma: clinical studies with sulfuric acid aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Utell, M.J.; Frampton, M.W.; Morrow, P.E. (University of Rochester School of Medicine and Dentistry, NY (United States))

    1991-11-01

    Until recently, acid deposition has been widely considered a serious ecological problem but not a threat to human health. The controlled clinical study is an important approach in linking acidic aerosol inhalation with respiratory effects. Asthmatic patients represent a subpopulation most responsive to sulfuric acid aerosols. In a series of studies with asthmatic volunteers, several factors have been identified that may modulate the intensity of the bronchoconstrictor response to inhaled acidic aerosols. We found (1) enhancement of the bronchoconstrictor response during exercise, (2) the more acidic aerosols provoke the greatest changes in lung function, and (3) mitigation of airway responses during sulfuric acid aerosol inhalation caused by high respiratory ammonia concentrations. Additional factors influencing responsiveness await identification.

  16. Internally mixed soot, sulfates, and organic matter in aerosol particles from Mexico City

    Directory of Open Access Journals (Sweden)

    K. Adachi

    2008-05-01

    Full Text Available Soot particles are major aerosol constituents that result from emissions of burning of fossil fuel and biomass. Because they both absorb sunlight and contribute to cloud formation, they are an influence on climate on local, regional, and global scales. It is therefore important to evaluate their optical and hygroscopic properties and those effects on the radiation budget. Those properties commonly change through reaction with other particles or gases, resulting in complex internal mixtures. Using transmission electron microscopy, we measured ~8000 particles (25 samples with aerodynamic diameters from 0.05 to 0.3 μm that were collected in March 2006 from aircraft over Mexico City (MC and adjacent areas. More than 50% of the particles consist of internally mixed soot, organic matter, and sulfate. Imaging combined with chemical analysis of individual particles show that many are coated, consist of aggregates, or both. Coatings on soot particles can amplify their light absorption, and coagulation with sulfates changes their hygroscopic properties, resulting in shorter lifetime. Our results suggest that a mixture of materials from multiple sources such as vehicles, power plants, and biomass burning occurs in individual particles, thereby increasing their complexity. Through changes in their optical and hygroscopic properties, internally mixed soot particles have a greater effect on the regional climate than uncoated soot particles. Moreover, soot occurs in more than 60% of all particles in the MC plumes, suggesting its important role in the formation of secondary aerosol particles.

  17. Sulfate Reduction at Low Ph To Remediate Acid Mine Drainage

    NARCIS (Netherlands)

    Sánchez-Andrea, I.; Sanz, J.L.; Bijmans, M.F.M.; Stams, A.J.M.

    2014-01-01

    Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities,

  18. Sulfate Reduction at Low Ph To Remediate Acid Mine Drainage

    NARCIS (Netherlands)

    Sánchez-Andrea, I.; Sanz, J.L.; Bijmans, M.F.M.; Stams, A.J.M.

    2014-01-01

    Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities, b

  19. Characterizing the influence of anthropogenic emissions and transport variability on sulfate aerosol concentrations at Mauna Loa Observatory

    Science.gov (United States)

    Potter, Lauren E.

    Sulfate aerosol in the atmosphere has substantial impacts on human health and environmental quality. Most notably, atmospheric sulfate has the potential to modify the earth's climate system through both direct and indirect radiative forcing mechanisms (Meehl et al., 2007). Emissions of sulfur dioxide, the primary precursor of sulfate aerosol, are now globally dominated by anthropogenic sources as a result of widespread fossil fuel combustion. Economic development in Asian countries since 1990 has contributed considerably to atmospheric sulfur loading, particularly China, which currently emits approximately 1/3 of global anthropogenic SO2 (Klimont et al., 2013). Observational and modeling studies have confirmed that anthropogenic pollutants from Asian sources can be transported long distances with important implications for future air quality and global climate change. Located in the remote Pacific Ocean (19.54°N, 155.58°W) at an elevation of 3.4 kilometers above sea level, Mauna Loa Observatory (MLO) is an ideal measurement site for ground-based, free tropospheric observations and is well situated to experience influence from springtime Asian outflow. This study makes use of a 14-year data set of aerosol ionic composition, obtained at MLO by the University of Hawaii at Manoa. Daily filter samples of total aerosol concentrations were made during nighttime downslope (free-tropospheric) transport conditions, from 1995 to 2008, and were analyzed for aerosol-phase concentrations of the following species: nitrate (NO3-), sulfate (SO42-), methanesulfonate (MSA), chloride (Cl-), oxalate, sodium (Na+), ammonium (NH 4+), potassium (K+), magnesium (Mg 2+), and calcium (Ca2+). An understanding of the factors controlling seasonal and interannual variations in aerosol speciation and concentrations at this site is complicated by the relatively short lifetimes of aerosols, compared with greenhouse gases which have also been sampled over long time periods at MLO. Aerosol filter

  20. Soluble species in the Arctic summer troposphere - Acidic gases, aerosols, and precipitation

    Science.gov (United States)

    Talbot, R. W.; Vijgen, A. S.; Harriss, R. C.

    1992-01-01

    The large-scale spatial distribution from 0.15-to 6 km altitude in the North American Arctic troposphere of several soluble acidic gases and major aerosol species during the summertime is reported. The distribution is found to be compositionally consistent on a large spatial scale. The summertime troposphere is an acidic environment, with HCOOH and CH3COOH the principal acidic gases while acidic sulfate aerosols dominate the particulate phase. There appears to be a surface source of NH3 over the pack ice which may originate from decay of dead marine organisms on the ice surface, evolution from surface ocean waters in open ice leads, or release from rotting sea ice. At low altitude over the pack ice this NH34 appears to partially neutralize aerosol acidity. Over sub-Arctic tundra in southeastern Alaska, inputs of marine biogenic sulfur from the Bering Sea appear to be an important source of boundary layer aerosol SO4(2-). The rainwater acidity over the tundra is typical of remote regions.

  1. Tales of volcanoes and El-Nino southern oscillations with the oxygen isotope anomaly of sulfate aerosol.

    Science.gov (United States)

    Shaheen, Robina; Abauanza, Mariana; Jackson, Teresa L; McCabe, Justin; Savarino, Joel; Thiemens, Mark H

    2013-10-29

    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher (17)O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and (17)O = 3.3‰, OEI = 11 and (17)O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that (17)O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations.

  2. Prenyl sulfates as alkylating reagents for mercapto amino acids.

    Science.gov (United States)

    Maltsev, Sergey; Sizova, Olga; Utkina, Natalia; Shibaev, Vladimir; Chojnacki, Tadeusz; Jankowski, Wieslaw; Swiezewska, Ewa

    2008-01-01

    A new methodology for prenylation of thiol compounds has been developed. The approach is based on the use of prenyl sulfates as new reagents for S-prenylation of benzenethiol and cysteamine in aqueous systems. The C(10)-prenols geraniol and nerol that differ in the configuration (E or Z, correspondingly) of the alpha-isoprene unit were efficiently O-sulfated in the presence of a pyridine-SO(3') complex. The obtained geranyl and neryl sulfates were tested as alkylating agents. These compounds were chosen to reveal the influence of the alpha-isoprene unit configuration on their alkylation (prenylation) ability. S-Geranyl cysteine was prepared to demonstrate the applicability of this method for prenylation of peptides containing mercapto amino acids.

  3. The Sectional Stratospheric Sulfate Aerosol module (S3A-v1) within the LMDZ general circulation model: description and evaluation against stratospheric aerosol observations

    Science.gov (United States)

    Kleinschmitt, Christoph; Boucher, Olivier; Bekki, Slimane; Lott, François; Platt, Ulrich

    2017-09-01

    Stratospheric aerosols play an important role in the climate system by affecting the Earth's radiative budget as well as atmospheric chemistry, and the capabilities to simulate them interactively within global models are continuously improving. It is important to represent accurately both aerosol microphysical and atmospheric dynamical processes because together they affect the size distribution and the residence time of the aerosol particles in the stratosphere. The newly developed LMDZ-S3A model presented in this article uses a sectional approach for sulfate particles in the stratosphere and includes the relevant microphysical processes. It allows full interaction between aerosol radiative effects (e.g. radiative heating) and atmospheric dynamics, including e.g. an internally generated quasi-biennial oscillation (QBO) in the stratosphere. Sulfur chemistry is semi-prescribed via climatological lifetimes. LMDZ-S3A reasonably reproduces aerosol observations in periods of low (background) and high (volcanic) stratospheric sulfate loading, but tends to overestimate the number of small particles and to underestimate the number of large particles. Thus, it may serve as a tool to study the climate impacts of volcanic eruptions, as well as the deliberate anthropogenic injection of aerosols into the stratosphere, which has been proposed as a method of geoengineering to abate global warming.

  4. Importance of including ammonium sulfate ((NH42SO4 aerosols for ice cloud parameterization in GCMs

    Directory of Open Access Journals (Sweden)

    R. Yang

    2010-02-01

    Full Text Available A common deficiency of many cloud-physics parameterizations including the NASA's microphysics of clouds with aerosol-cloud interactions (hereafter called McRAS-AC is that they simulate lesser (larger than the observed ice cloud particle number (size. A single column model (SCM of McRAS-AC physics of the GEOS4 Global Circulation Model (GCM together with an adiabatic parcel model (APM for ice-cloud nucleation (IN of aerosols were used to systematically examine the influence of introducing ammonium sulfate (NH42SO4 aerosols in McRAS-AC and its influence on the optical properties of both liquid and ice clouds. First an (NH42SO4 parameterization was included in the APM to assess its effect on clouds vis-à-vis that of the other aerosols. Subsequently, several evaluation tests were conducted over the ARM Southern Great Plain (SGP and thirteen other locations (sorted into pristine and polluted conditions distributed over marine and continental sites with the SCM. The statistics of the simulated cloud climatology were evaluated against the available ground and satellite data. The results showed that inclusion of (NH42SO4 into McRAS-AC of the SCM made a remarkable improvement in the simulated effective radius of ice cloud particulates. However, the corresponding ice-cloud optical thickness increased even more than the observed. This can be caused by lack of horizontal cloud advection not performed in the SCM. Adjusting the other tunable parameters such as precipitation efficiency can mitigate this deficiency. Inclusion of ice cloud particle splintering invoked empirically further reduced simulation biases. Overall, these changes make a substantial improvement in simulated cloud optical properties and cloud distribution particularly over the Intertropical Convergence Zone (ITCZ in the GCM.

  5. 75 FR 78243 - Propionic Acid and Salts, Urea Sulfate, Methidathion, and Methyl Parathion; Registration Review...

    Science.gov (United States)

    2010-12-15

    ... AGENCY Propionic Acid and Salts, Urea Sulfate, Methidathion, and Methyl Parathion; Registration Review... pesticides propionic acid and salts, case no. 4078, urea sulfate, case no. 7213, methidathion, case no. 0034... pesticides in the table below--propionic acid and salts, case 4078, urea sulfate, case no. 7213,...

  6. Direct shortwave forcing of climate by anthropogenic sulfate aerosol: Sensitivity to particle size, composition, and relative humidity

    Energy Technology Data Exchange (ETDEWEB)

    Nemesure, S.; Wagener, R.; Schwartz, S.E. [Brookhaven National Lab., Upton, New York (United States)

    1996-04-01

    Recent estimates of global or hemispheric average forcing of climate by anthropogenic sulfate aerosol due to scattering of shortwave radiation are uncertain by more than a factor of 2. This paper examines the sensitivity of forcing to these microphysical properties for the purposes of obtaining a better understanding of the properties required to reduce the uncertainty in the forcing.

  7. The optical constants of several atmospheric aerosol species - Ammonium sulfate, aluminum oxide, and sodium chloride

    Science.gov (United States)

    Toon, O. B.; Pollack, J. B.; Khare, B. N.

    1976-01-01

    An investigation is conducted of problems which are related to a use of measured optical constants in the simulation of the optical constants of real atmospheric aerosols. The techniques of measuring optical constants are discussed, taking into account transmission measurements through homogeneous and inhomogeneous materials, the immersion of a material in a liquid of a known refractive index, the consideration of the minimum deviation angle of prism measurement, the interference of multiply reflected light, reflectivity measurements, and aspects of mathematical analysis. Graphs show the real and the imaginary part of the refractive index as a function of wavelength for aluminum oxide, NaCl, and ammonium sulfate. Tables are provided for the dispersion parameters and the optical constants.

  8. Effects of polyacrylic acid additive on barium sulfate particle morphology

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jie; Liu, Dandan; Jiang, Hongkun; Wang, Jun; Jing, Xiaoyan; Chen, Rongrong [Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Zhu, Wenting [Department of Gastroenterology, Harbin Medical University Cancer Hospital, Harbin 150081 (China); Han, Shihui [Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Li, Wanyou [College of Power and Energy Engineering, Harbin Engineering University, Harbin 150001 (China); Wei, Hao, E-mail: weihao7512@126.com [Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); College of Power and Energy Engineering, Harbin Engineering University, Harbin 150001 (China)

    2016-06-01

    In this paper, polyacrylic acid (PAA) was used as a growth modifier to control micron-sized barium sulfate particles via a simple precipitation reaction between sodium sulfate and barium chloride at ambient temperature. The barium sulfate particles were exhibited various morphologies, such as monodisperse spheres, ellipsoids, rose-like aggregates, etc. To better understand the formation mechanisms of the various morphologies of these particles, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermo-gravimetric analysis (TGA) were employed. It was found that the PAA concentration, pH, and Ba{sup 2+} and SO{sub 4}{sup 2−} ions concentrations were the most important parameters controlling the morphology of the BaSO{sub 4} particles. These parameters affected the BaSO{sub 4} morphology by influencing the interactions between the PAA carboxyl groups and inorganic ions and the conformation change of the PAA molecular chains. Moreover, this work attempts to provide a preliminary understanding of the formation of the spherical BaSO{sub 4} particles with the randomly coiled conformation of the polymer. - Highlights: • Polyacrylic acid (PAA) was used as a growth modifier to control micron-sized BaSO{sub 4} particles. • The PAA/BaSO{sub 4} particles were exhibited various morphologies. • Provide a preliminary understanding of the formation mechanism of BaSO{sub 4} particles.

  9. Sensitivity of modelled sulfate aerosol and its radiative effect on climate to ocean DMS concentration and air-sea flux

    Science.gov (United States)

    Tesdal, Jan-Erik; Christian, James R.; Monahan, Adam H.; von Salzen, Knut

    2016-09-01

    Dimethylsulfide (DMS) is a well-known marine trace gas that is emitted from the ocean and subsequently oxidizes to sulfate in the atmosphere. Sulfate aerosols in the atmosphere have direct and indirect effects on the amount of solar radiation reaching the Earth's surface. Thus, as a potential source of sulfate, ocean efflux of DMS needs to be accounted for in climate studies. Seawater concentration of DMS is highly variable in space and time, which in turn leads to high spatial and temporal variability in ocean DMS emissions. Because of sparse sampling (in both space and time), large uncertainties remain regarding ocean DMS concentration. In this study, we use an atmospheric general circulation model with explicit aerosol chemistry (CanAM4.1) and several climatologies of surface ocean DMS concentration to assess uncertainties about the climate impact of ocean DMS efflux. Despite substantial variation in the spatial pattern and seasonal evolution of simulated DMS fluxes, the global-mean radiative effect of sulfate is approximately linearly proportional to the global-mean surface flux of DMS; the spatial and temporal distribution of ocean DMS efflux has only a minor effect on the global radiation budget. The effect of the spatial structure, however, generates statistically significant changes in the global-mean concentrations of some aerosol species. The effect of seasonality on the net radiative effect is larger than that of spatial distribution and is significant at global scale.

  10. Free amino acids in Antarctic aerosol: potential markers for the evolution and fate of marine aerosol

    Directory of Open Access Journals (Sweden)

    E. Barbaro

    2015-01-01

    Full Text Available To investigate the impact of marine aerosols on global climate change it is important to study their chemical composition and size distribution. Amino acids are a component of the organic nitrogen in aerosols, particles containing amino acids have been found to be efficient ice nuclei. The main aim of this study was to investigate the L- and D-free amino acid composition as possible tracers of primary biological production in Antarctic aerosols from three different areas: two continental bases, Mario Zucchelli Station (MZS on the coast of the Ross Sea, Concordia Station at Dome C on the Antarctic Plateau, and the Southern Ocean near the Antarctic continent. Studying the size distribution of amino acids in aerosols allowed us to characterize this component of the water-soluble organic carbon (WSOC in marine aerosols near their source and after long-range transport. The presence of only free L-amino acids in our samples is indicative of the prevalence of phytoplanktonic material. Sampling at these three points allowed us to study the reactivity of these compounds during long-range transport. The mean total amino acid concentration detected at MZS was 11 pmol m−3, a higher percentage of amino acids were found in the fine fraction. The aerosol samples collected at Dome C had the lowest amino acid values (0.7 and 0.8 pmol m−3 and the coarse particles were found to be enriched with amino acids compared to the coastal site. The amino acid composition had also changed suggesting that physical and chemical transformations had occurred during long range transport. During the sampling cruise on the R/V talica on the Southern Ocean, high concentrations of amino acids were found in the total suspended particles, this we attribute to the presence of intact biological material in the sample.

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

    Science.gov (United States)

    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

  12. Estimation of interfacial acidity of sodium dodecyl sulfate micelles

    Indian Academy of Sciences (India)

    Arghya Dey; G Naresh Patwari

    2011-11-01

    An enhancement in the excited state proton transfer (ESPT) processes of coumarin-102 (C-102) dye was observed upon addition of salicylic acid and hydrochloric acid in sodium dodecyl sulfate (SDS) micellar solution. The phenomenon was observed only in the micellar medium of anionic surfactant SDS and not in case of cationic (CTAB) or neutral (Trition X -100) surfactants. ESPT of C-102 was also observed in aqueous solutions but on addition of very high concentrations of hydrochloric acid. However, on comparing the ratio of the protonated species from the emission spectra in the presence and absence of SDS micelle, a conclusive estimation of the local proton concentration at the Stern layer of SDS micelles could be evaluated.

  13. Smectite Formation in Acid Sulfate Environments on Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Clark, J. V.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

  14. Study on Dicarboxylic Acids in Aerosol Samples with Capillary Electrophoresis

    Directory of Open Access Journals (Sweden)

    Heidi Adler

    2014-01-01

    Full Text Available The research was performed to study the simultaneous detection of a homologous series of α, ω-dicarboxylic acids (C2–C10, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic acids, with capillary electrophoresis using indirect UV detection. Good separation efficiency in 2,6-pyridinedicarboxylic acid as background electrolyte modified with myristyl trimethyl ammonium bromide was obtained. The dicarboxylic acids were ionised and separated within five minutes. For the study, authentic samples were collected onto dry cellulose membrane filters of a cascade impactor (12 stages from outdoor spring aerosols in an urban area. Hot water and ultrasonication extraction methods were used to isolate the acids from membrane filters. Due to the low concentrations of acids in the aerosols, the extracts were concentrated with solid-phase extraction (SPE before determination. The enrichment of the carboxylic acids was between 86 and 134% with sample pretreatment followed by 100-time increase by preparation of the sample to 50 μL. Inaccuracy was optimised for all the sample processing steps. The aerosols contained dicarboxylic acids C2–C10. Then, mostly they contained C2, C5, and C10. Only one sample contained succinic acid. In the study, the concentrations of the acids in aerosols were lower than 10 ng/m3.

  15. Study of pH Stability of R-Salbutamol Sulfate Aerosol Solution and Its Antiasthmatic Effects in Guinea Pigs.

    Science.gov (United States)

    Liu, Qing; Li, Qingrui; Han, Ting; Hu, Tingting; Zhang, Xuemei; Hu, Junhua; Hu, Hui; Tan, Wen

    2017-09-01

    Currently, all commercial available nebulized salbutamol in China is in its racemic form. It is known that only R-salbutamol (eutomer) has therapeutic effects, while S-salbutamol (distomer) may exacerbate asthma after chronic use. Therefore, it is an unmet clinical need to develop R-salbutamol as a nebulized product that is more convenient for young and old patients. In our study, a stable aerosol solution of R-salbutamol sulfate was established, and its antiasthmatic effects were confirmed. The decomposition rate and racemization effect of the R-salbutamol sulfate solution were evaluated over a pH range from 1 to 10 (except pH=7, 8) at 60°C. The aerodynamic particle size of the R-salbutamol sulfate solution and commercial RS-salbutamol sulfate solution were both tested in vitro by Next-Generation Impactor (NGI) in 5°C. Laser diffractometer was used to characterize the droplet-size distribution (DSD) of both solutions. We next conducted an in vivo animal study to document the antiasthmatic effect of R-salbutamol aerosol sulfate solution and determine the relationship to RS-salbutamol. The results showed that the R-salbutamol sulfate solution was more stable at pH 6. In vitro comparison studies indicated that there was no distribution difference between R-salbutamol sulfate solution and the commercial RS-salbutamol solution. The animal results showed that R-salbutamol was more potent than RS-salbutamol against the same dose of histamine challenge. Unlike commercial RS-salbutamol, which was acidified to a pH of 3.5 to extend bench life but may cause bronchoconstriction in asthmatic patients, the neutralized R-salbutamol solution was more suitable for clinic use.

  16. Glacier evolution in high-mountain Asia under stratospheric sulfate aerosol injection geoengineering

    Science.gov (United States)

    Zhao, Liyun; Yang, Yi; Cheng, Wei; Ji, Duoying; Moore, John C.

    2017-06-01

    Geoengineering by stratospheric sulfate aerosol injection may help preserve mountain glaciers by reducing summer temperatures. We examine this hypothesis for the glaciers in high-mountain Asia using a glacier mass balance model driven by climate simulations from the Geoengineering Model Intercomparison Project (GeoMIP). The G3 and G4 schemes specify use of stratospheric sulfate aerosols to reduce the radiative forcing under the Representative Concentration Pathway (RCP) 4.5 scenario for the 50 years between 2020 and 2069, and for a further 20 years after termination of geoengineering. We estimate and compare glacier volume loss for every glacier in the region using a glacier model based on surface mass balance parameterization under climate projections from three Earth system models under G3, five models under G4, and six models under RCP4.5 and RCP8.5. The ensemble projections suggest that glacier shrinkage over the period 2010-2069 is equivalent to sea-level rise of 9.0 ± 1.6 mm (G3), 9.8 ± 4.3 mm (G4), 15.5 ± 2.3 mm (RCP4.5), and 18.5 ± 1.7 mm (RCP8.5). Although G3 keeps the average temperature from increasing in the geoengineering period, G3 only slows glacier shrinkage by about 50 % relative to losses from RCP8.5. Approximately 72 % of glaciated area remains at 2069 under G3, as compared with about 30 % for RCP8.5. The widely reported reduction in mean precipitation expected for solar geoengineering is unlikely to be as important as the temperature-driven shift from solid to liquid precipitation for forcing Himalayan glacier change. The termination of geoengineering at 2069 under G3 leads to temperature rise of about 1.3 °C over the period 2070-2089 relative to the period 2050-2069 and corresponding increase in annual mean glacier volume loss rate from 0.17 to 1.1 % yr-1, which is higher than the 0.66 % yr-1 under RCP8.5 during 2070-2089.

  17. Glacier evolution in high-mountain Asia under stratospheric sulfate aerosol injection geoengineering

    Directory of Open Access Journals (Sweden)

    L. Zhao

    2017-06-01

    Full Text Available Geoengineering by stratospheric sulfate aerosol injection may help preserve mountain glaciers by reducing summer temperatures. We examine this hypothesis for the glaciers in high-mountain Asia using a glacier mass balance model driven by climate simulations from the Geoengineering Model Intercomparison Project (GeoMIP. The G3 and G4 schemes specify use of stratospheric sulfate aerosols to reduce the radiative forcing under the Representative Concentration Pathway (RCP 4.5 scenario for the 50 years between 2020 and 2069, and for a further 20 years after termination of geoengineering. We estimate and compare glacier volume loss for every glacier in the region using a glacier model based on surface mass balance parameterization under climate projections from three Earth system models under G3, five models under G4, and six models under RCP4.5 and RCP8.5. The ensemble projections suggest that glacier shrinkage over the period 2010–2069 is equivalent to sea-level rise of 9.0 ± 1.6 mm (G3, 9.8 ± 4.3 mm (G4, 15.5 ± 2.3 mm (RCP4.5, and 18.5 ± 1.7 mm (RCP8.5. Although G3 keeps the average temperature from increasing in the geoengineering period, G3 only slows glacier shrinkage by about 50 % relative to losses from RCP8.5. Approximately 72 % of glaciated area remains at 2069 under G3, as compared with about 30 % for RCP8.5. The widely reported reduction in mean precipitation expected for solar geoengineering is unlikely to be as important as the temperature-driven shift from solid to liquid precipitation for forcing Himalayan glacier change. The termination of geoengineering at 2069 under G3 leads to temperature rise of about 1.3 °C over the period 2070–2089 relative to the period 2050-2069 and corresponding increase in annual mean glacier volume loss rate from 0.17 to 1.1 % yr−1, which is higher than the 0.66 % yr−1 under RCP8.5 during 2070–2089.

  18. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

    Science.gov (United States)

    Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

    2014-08-19

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

  19. 75 FR 51055 - Propionic Acid and Salts, and Urea Sulfate; Registration Review Proposed Decisions; Notice of...

    Science.gov (United States)

    2010-08-18

    ... AGENCY Propionic Acid and Salts, and Urea Sulfate; Registration Review Proposed Decisions; Notice of... urea sulfate and opens a public comment period on the proposed decisions. Registration review is EPA's.... Urea sulfate is used as a desiccant on ] cotton. No food crop uses remain and all tolerances for...

  20. A simplified method for estimation of jarosite and acid-forming sulfates in acid mine wastes.

    Science.gov (United States)

    Li, Jun; Smart, Roger St C; Schumann, Russell C; Gerson, Andrea R; Levay, George

    2007-02-01

    In acid base accounting (ABA) estimates of acid mine wastes, the acid potential (AP) estimate can be improved by using the net carbonate value (NCV) reactive sulfide S method rather than total S assay methods but this does not give recovery of potentially acid producing ferrous and ferric sulfates present in many wastes. For more accurate estimation of AP, an effective, site-specific method to quantify acid sulfate salts, such as jarosite and melanterite, in waste rocks has been developed and tested on synthetic and real wastes. The SPOCAS (acid sulfate soils) methods have been modified to an effective, rapid method to speciate sulfate forms in different synthetic waste samples. A three-step sequential extraction procedure has been established. These steps are: (1) argon-purged water extraction (3 min) to extract soluble Fe(II) salts (particularly melanterite), epsomite and gypsum (1 wt.% S) as copper sulfides, the second step of roasting needs to be excluded from the procedure with an increased time of 4 M HCl extraction to 16 h for jarosite determination.

  1. Characteristics of Soluble and Exchangeable Acidity in an Extremely Acidified Acid Sulfate Soil

    Institute of Scientific and Technical Information of China (English)

    C.Lin; M.D.MELVILLE; 等

    1999-01-01

    An extremely acidified acid sulfate soil(ASS) was investigated to characterise its soluble and exchangeable acidity,The results showed that soluble acidity of a sample dtermined by titration with a KOH soulution was much significantly greater than that indicated by pH measured using a pH meter,paricularly for the extremely acidic soil samples,This is because the total soluble acidity of the extremely acidic soil samples was mainly composed of various soluble Al and Fe species,possibly in forms of Al sulfate complexes(e.g.,AlSO4+) and feerous Fe(Fe2+)_,It is therefore suggested not to use pH alone as an indicator of soluble acidity in ASS,particularly for extremely acidic ASS,It is also likely that AlSO4+ actively participated in cation exchange reactions.It appears that the possible involvement of this Al sulfate cation in the cation adsorption has significant effect on increasing the amount of acidity being adsorbed by the soils.

  2. Sulfur-rich geothermal emissions elevate acid aerosol levels in metropolitan Taipei.

    Science.gov (United States)

    Lin, Chih-Hung; Mao, I-Fang; Tsai, Pei-Hsien; Chuang, Hsin-Yi; Chen, Yi-Ju; Chen, Mei-Lien

    2010-08-01

    Several studies have demonstrated that millions of people globally are potentially exposed to volcanic gases. Hydrogen sulfide is a typical gas in volcanic and geothermal areas. The gas is toxic at high concentrations that predominantly affects the nervous, cardiovascular, and respiratory systems. The WHO air quality guideline for hydrogen sulfide is 150 microg m(-3) (105 ppb). The northwest part of Taipei is surrounded by sulfur-rich geothermal and hot springs. Active fumaroles and bubbling springs around the geothermal area emit acidic gases. In combination with automobile emissions, the pollution of acid aerosols is characteristic of the metropolis. This study considered sulfur-rich geothermal, suburban and downtown locations of this metropolis to evaluate geothermally emitted acid aerosol and H(2)S pollution. Acid aerosols were collected using a honeycomb denuder filter pack sampling system (HDS), and then analyzed by ion chromatography (IC). Results indicated that long-term geothermal emissions, automobile emissions and photochemical reactions have led to significant variations in air pollution among regions of metropolitan Taipei. The highest H(2)S concentration was 1705 ppb in the geothermal area with low traffic density and the mean concentration was 404.06 ppb, which was higher than WHO guideline and might cause eye irritation. The SO(2) concentrations were relatively low (mean concentration was 3.9 ppb) in this area. It may partially result from the chemical reduction reaction in the geothermal emission, which converted the SO(2) gas into SO(4)(2-) and H(2)S. Consequently, very high sulfate concentrations (mean concentration higher than 25.0 microg m(-3)) were also observed in the area. The geothermal areas also emitted relatively high levels of aerosol acidity, Cl(-), F(-), PO(4)(3-), and N-containing aerosols. As a result, concentrations of HNO(3), NO(2)(-), PO(4)(3-), and SO(4)(2-) in metropolitan Taipei are significantly higher than those in other

  3. Fingerprinting Volcanic and Anthropogenic Sulfur Dioxide in the Air: A 25 Year Record of Sulfate Aerosols from the South Pole Snowpit, Antarctica

    Science.gov (United States)

    Shaheen, R.; Abaunza-Quintero, M.; Jackson, T. L.; McCabe, J.; Savarino, J. P.; Thiemens, M. H.

    2012-12-01

    Sulfate aerosols, unlike greenhouse gases, cause cooling effect (-0.4 ± 0.2 W.m-2) by scattering incoming solar radiation and by acting as cloud condensation nuclei (IPCC 2007). Volcanic eruptions with explosivity Indices >5 inject large amounts of SO2 and particles into the stratosphere causing a significant decrease in temperature. For example a 0.7oC decrease in Earth's temperature was observed following the Pinatubo eruption in 1991. Stratospheric injection of sulfate aerosols has been suggested as a geoengineering effort to mitigate global warming caused by a significant increase in greenhouse gases. To understand the impact of volcanic events on the stratospheric sulfate aerosol layer and subsequent changes in the dynamics of the upper atmosphere, a long term and high temporal resolution record of sulfate aerosol is needed. Here we present a 25 year (1978 to 2003) high resolution record of sulfate aerosols which covers largest volcanic eruptions of the 20th century namely, El-Chichón 1982 and Pinatubo 1991. Sulfate aerosol samples were obtained from a 1x1m snowpit at the South Pole, Antarctica with approximately 6 month time steps. Sulfate concentrations vary from 30 to 70 ppb depending on the season with exceptions during volcanic events which contributed a three to four folds increase in sulfate concentration Sulfate concentrations of120 ppb following El Chichón and 190 ppb after Pinatubo eruptions were observed. The oxygen isotopic anomaly varied from 0.7‰ to 3.9‰ with the highest anomaly occurring after the Pinatubo eruption. The positive Δ17O of sulfate derives from aqueous phase oxidation of SO2 by H2O2 and O3 oxidation and involves transfer of the isotopic anomaly from the oxidant to the product sulfate. Coupled with kinetic analysis the relative reaction rates the relative proportions of oxidation can be calculated. All other sulfate sources such as sea salt sulfates, primary sulfates from fossil fuel combustion, metal catalyzed oxidation of S

  4. Acidity enhancement of niobia by sulfation: An experimental and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rocha, Angela S., E-mail: angela.sanches.rocha@gmail.com [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Costa, Gustavo C. [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B. [Universidade Federal do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil)

    2017-01-15

    Acidic solids are used as catalyst at several industrial processes and studies to improve their activities have been developed by different groups. One method well known is sulfating oxide to create new acid sites, but investigations about sulfated niobia are still scarce. This work studied the influence of sulfation on the niobia acidity by using a very simple reaction model, the esterification of acetic acid with ethanol, performed at 60 °C and 1 atm. Niobia and sulfated niobia samples were characterized by N{sub 2} adsorption, X-ray diffraction, FTIR and titration with n-butylamine. To investigate the nature of sulfate groups formed on the surface of niobia, calculations based on the Density Functional Theory (DFT) have been performed for two models: pure niobia with hydroxylated surface and sulfated niobia where one OH{sup −} surface group was replaced by a HSO{sub 4}{sup −}. The experimental results indicated that the sulfation treatment leads to an increase in the specific surface area, acidity and, consequently, in the activity of niobia, with small changes in the crystal structure of the solid. The presence of sulfate groups was evidenced by FTIR spectra and calculations have indicated HSO{sub 4}{sup −} species bounded to the surface. Density Functional Perturbation Theory (DFPT) was also employed to obtain infrared intensities in the region of sulfate vibration bands. - Highlights: • Sulfation treatment has improved the acidity of niobium oxide. • A sulfate group on niobia (T-Nb{sub 2}O{sub 5}) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

  5. Reclamation of acid sulfate soils using lime-stabilized biosolids.

    Science.gov (United States)

    Orndorff, Zenah W; Daniels, W Lee; Fanning, Delvin S

    2008-01-01

    Excavation of sulfidic materials during construction has resulted in acid rock drainage (ARD) problems throughout Virginia. The most extensive documented uncontrolled disturbance at a single location is Stafford Regional Airport (SRAP) in Stafford, Virginia. Beginning in 1998, over 150 ha of sulfidic Coastal Plain sediments were disturbed, including steeply sloping cut surfaces and spoils placed into fills. Acid sulfate soils developed, and ARD generated on-site degraded metal and concrete structures and heavily damaged water quality with effects noted over 1 km downstream. The site was not recognized as sulfidic until 2001 when surface soil sampling revealed pH values ranging from 1.9 to 5.3 and peroxide potential acidity (PPA) values ranging from 1 to 42 Mg CaCO(3) per 1000 Mg material. In February 2002 a water quality program was established in and around the site to monitor baseline pH, EC, NO(3)-N, NH(4)-N, PO(4)-P, Fe, Al, Mn, and SO(4)-S, and initial pH values as low as 2.9 were noted in on-site receiving streams. In the spring and fall of 2002, the site was treated with variable rates of lime-stabilized biosolids, straw-mulch, and acid- and salt-tolerant legumes and grasses. By October 2002, the site was fully revegetated (> or = 90% living cover) with the exception of a few highly acidic outcrops and seepage areas. Surface soil sampling in 2003, 2004, and 2006 revealed pH values typically > 6.0. Water quality responded quickly to treatment, although short-term NH(4)(+) release occurred. Despite heavy loadings, no significant surface water P losses were observed.

  6. Acid sulfate soils are an environmental hazard in Finland

    Science.gov (United States)

    Pihlaja, Jouni

    2016-04-01

    Acid sulfate soils (ASS) create significant threats to the environment on coastal regions of the Baltic Sea in Finland. The sediments were deposited during the ancient Litorina Sea phase of the Baltic Sea about 7500-4500 years ago. Finland has larger spatial extent of the ASS than any other European country. Mostly based on anthropogenic reasons (cultivation, trenching etc.) ASS deposits are currently being exposed to oxygen which leads to chemical reaction creating sulfuric acid. The acidic waters then dissolve metals form the soil. Acidic surface run off including the metals are then leached into the water bodies weakening the water quality and killing fish or vegetation. In constructed areas acidic waters may corrode building materials. Geological Survey of Finland (GTK) is mapping ASS deposits in Finland. The goal is to map a total of 5 million hectares of the potentially ASS affected region. It has been estimated that the problematic Litorina Sea deposits, which are situated 0-100 m above the recent Baltic Sea shoreline, cover 500 000 hectares area. There are several phases in mapping. The work begins at the office with gathering the existing data, interpreting airborne geophysical data and compiling a field working plan. In the field, quality of the soil is studied and in uncertain cases samples are taken to laboratory analyses. Also electrical conductivity and pH of soil and water are measured in the field. Laboratory methods include multielemental determinations with ICP-OES, analyses of grain size and humus content (LOI), and incubation. So far, approximately 60 % of the potential ASS affected regions in Finland are mapped. Over 15 000 sites have been studied in the field and 4000 laboratory analyses are done. The spatial database presented in the scale of 1: 250 000 can be viewed at the GTK's web pages (http://gtkdata.gtk.fi/hasu/index.html).

  7. Dermatan Sulfate Epimerase 1-Deficient Mice Have Reduced Content and Changed Distribution of Iduronic Acids in Dermatan Sulfate and an Altered Collagen Structure in Skin

    DEFF Research Database (Denmark)

    Maccarana, M.; Kalamajski, S.; Kongsgaard, M.;

    2009-01-01

    Dermatan sulfate epimerase 1 (DS-epi1) and DS-epi2 convert glucuronic acid to iduronic acid in chondroitin/dermatan sulfate biosynthesis. Here we report on the generation of DS-epi1-null mice and the resulting alterations in the chondroitin/dermatan polysaccharide chains. The numbers of long blocks...... of adjacent iduronic acids are greatly decreased in skin decorin and biglycan chondroitin/dermatan sulfate, along with a parallel decrease in iduronic-2-O-sulfated-galactosamine-4-O-sulfated structures. Both iduronic acid blocks and iduronic acids surrounded by glucuronic acids are also decreased in versican......-derived chains. DS-epi1-deficient mice are smaller than their wild-type littermates but otherwise have no gross macroscopic alterations. The lack of DS-epi1 affects the chondroitin/dermatan sulfate in many proteoglycans, and the consequences for skin collagen structure were initially analyzed. We found...

  8. Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

    Science.gov (United States)

    Morris, R. V.; Catalano, J. G.; Klingelhoefer, G.; Schroeder, C.; Gellert, R.; Clark, B. C.; Ming, D. W.; Yen, A. S.; Arvidson, R. E.; Cohen, B. A.; hide

    2017-01-01

    The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

  9. Acid Release from an Acid Sulfate Soil Sample Under Successive Extractions with Different Extractants

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An acid sulfate soil sample was successively extracted with deionized water, 1 mol L-1 KCI and 0.000 5 mol L-1 Ca(OH)2 solutions. The results showed that only very small amounts of acidity were extracted by deionized water, possibly through slow jarosite hydrolysis. Acid release through jarosite hydrolysis was greatly enhanced by Ca(OH)2 extraction at the expense of the added OH- being neutralized by the acid released. Successive extraction of the sample with KCI removed the largest amounts of acidity from the sample. However, it is likely that the major form of acidity released by KC1 extraction was exchangeable acidity. The results also show the occurrence of low or non charged A1 and Fe species in water and Ca(OH)2 extracts after first a few extractions. It appears that such a phenomenon was related to a decreasing EC value with increasing number of extractions.

  10. Aerosol volatility and enthalpy of sublimation of carboxylic acids.

    Science.gov (United States)

    Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

    2010-04-08

    The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

  11. Fingerprinting El Nino Southern Ocean events using oxygen triple isotopic composition of aerosol sulfate from the South Pole snow pit samples

    Science.gov (United States)

    Thiemens, M. H.; Abaunza Quintero, M. M.; Shaheen, R.; Jackson, T. L.; McCabe, J.; Savarino, J. P.

    2011-12-01

    According to the Intergovernmental Panel on Climate Change 4th assessment report [IPCC 2007], aerosols are the largest source of uncertainty in modeling the earth's radiative budget. Sulfate aerosols contributes to global cooling that may mask warming effect by greenhouse gases, therefore, high resolution record of aerosol sulfate can help to understand the impact of anthropogenic activities and natural variations on climate change. Sulfate aerosols were extracted from the ice pit samples obtained from the South Pole (1979-2002) at a high resolution temporal record of the winter and summer seasons. To insure highest measurement ability of very small samples (few nano moles) a hydrogen peroxide cleaning method was developed to remove organic impurities from aerosols which otherwise significantly affect O-triple isotopic measurement of the sulfates. Preliminary data indicated non sea salt contributions of 70-95% with a range in δ18OVSMOW = -1.86 -12% and Δ17O = 0.8-3.7% for the years 1990-2001. The positive Δ17O of sulfate derives from aqueous phase oxidation of SO2 by H2O2 and O3 and involves transfer of the isotopic anomaly from the oxidant to the product sulfate. All other sulfate sources (sea salt sulfates and primary sulfates from fossil fuel combustion), including gas-phase oxidation by OH in the troposphere, metal catalyzed oxidation of S(IV) to S(VI), are strictly mass dependent (Δ17O = 0%). The magnitude of the transfer of the Δ17O varies according to the relative contribution from H2O2 at pH 6 (Δ17O = 8%). Seasonal variations of these oxidants and their contribution to S(IV) oxidation will be discussed. Since our samples include the time period 1977-2002, each year divided into two parts (winter and summer season's aerosols), in addition to seasonal variation in sulfate oxidation pathways, we may also be able to assess if the oxidation cycle of sulfate changes during El Niño years.

  12. The NH4+-NO3--Cl--SO42--H2O aerosol system and its gas phase precursors at a pasture site in the Amazon Basin: How relevant are mineral cations and soluble organic acids?

    NARCIS (Netherlands)

    Trebs, I.; Metzger, S.; Meixner, F.X.; Helas, G.N.; Hoffer, A.; Rudich, Y.; Falkovich, A.H.; Moura, M.A.L.; Silva, da R.S.; Artaxo, P.; Slanina, J.; Andreae, M.O.

    2005-01-01

    Real-time measurements of ammonia, nitric acid, hydrochloric acid, sulfur dioxide and the water-soluble inorganic aerosol species, ammonium, nitrate, chloride, and sulfate were performed at a pasture site in the Amazon Basin (Rondônia, Brazil). The measurements were made during the late dry season (

  13. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    Directory of Open Access Journals (Sweden)

    A. W. Birdsall

    2014-08-01

    Full Text Available Recently, methacrylic acid epoxide (MAE has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA: 2-methylglyceric acid (2-MG and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG, and acids (including MAE and 2-MG in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water; this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  14. Measurement of aerosol sulfuric acid 2. Pronounced layering in the free troposphere during the second Aerosol Characterization Experiment (ACE 2)

    NARCIS (Netherlands)

    Curtius, J; Sierau, B; Arnold, F; de Reus, M; Strom, J; Scheeren, HA; Lelieveld, J

    2001-01-01

    Measurements of aerosol sulfuric acid in the free troposphere were performed in the vicinity of Tenerife, Canary Islands (28degreesN, 16degreesW), in July 1997. These measurements were carried out on board a Dutch Cessna Citation 11 research aircraft within the framework of the second Aerosol Charac

  15. Organosulfates and organic acids in Arctic aerosols: speciation, annual variation and concentration levels

    Directory of Open Access Journals (Sweden)

    A. M. K. Hansen

    2014-02-01

    , organosulfate and organic acid concentrations remained relatively constant during most of the year at amean concentration of 15 (±4 ng m−3 (accounting for 4 (±1% of total organic matter and 3.9 (±1 ng m−3 (accounting for 1.1 (±0.1% of total organic matter respectively. However during four weeks of spring remarkably higher concentrations of total organosulfates (23–36 ng m−3 and total organic acids (7–10 ng m−3 were observed. The periods of observed elevated organosulfate and organic acid concentration at Station Nord and at Zeppelin Mountain coincided with the Arctic Haze period. Furthermore, backwards air mass trajectories indicated northern Eurasia as the main source region of the Arctic haze aerosols at both sites. Periods with air mass transport from Russia to Zeppelin Mountain were associated with a doubled number of detected organosulfate species compared with periods of air mass transport from the Arctic Ocean, Scandinavia and Greenland. Our analysis showed the presence of organosulfates and organic acids of both biogenic and anthropogenic origin throughout the year at both Arctic sites. As the formation of organosulfates binds inorganic sulfate, their presence may possibly affect the formation and lifetime of clouds in the Arctic atmosphere.

  16. COS in the stratosphere. [sulfuric acid aerosol precursor

    Science.gov (United States)

    Inn, E. C. Y.; Vedder, J. F.; Tyson, B. J.; Ohara, D.

    1979-01-01

    Carbonyl sulfide (COS) has been detected in the stratosphere, and mixing ratio measurements are reported for altitudes of 15.2 to 31.2 km. A large volume, cryogenic sampling system mounted on board a U-2 aircraft has been used for lower stratosphere measurements and a balloon platform for measurement at 31.2 km. These observations and measurements strongly support the concept that stratospheric COS is an important precursor in the formation of sulfuric acid aerosols.

  17. A study of uncertainties in the sulfate distribution and its radiative forcing associated with sulfur chemistry in a global aerosol model

    Directory of Open Access Journals (Sweden)

    D. Goto

    2011-04-01

    Full Text Available The direct radiative forcing by sulfate aerosols is still uncertain, mainly because the uncertainties are largely derived from differences in sulfate column burdens and its vertical distributions among global aerosol models. One of possible reasons of the large difference in the computed values is that the radiative forcing delicately depends on various simplifications of the sulfur processes made in the models. In this study, therefore, we investigated impacts of different parts of the sulfur chemistry module in a global aerosol model, SPRINTARS, on the sulfate distribution and its radiative forcing. Important studies were effects of simplified and more physical-based sulfur processes in terms of treatment of sulfur chemistry, oxidant chemistry, and dry deposition process of sulfur components. The results showed that the difference in the aqueous-phase sulfur chemistry among these treatments has the largest impact on the sulfate distribution. Introduction of all the improvements mentioned above brought the model values noticeably closer to in-situ measurements than those in the simplified methods used in the original SPRINTARS model. At the same time, these improvements also led the computed sulfate column burdens and its vertical distributions in good agreement with other AEROCOM model values. The global annual mean radiative forcings due to aerosol direct effect of anthropogenic sulfate was thus estimated to be −0.3 W m−2, whereas the original SPRINTARS model showed −0.2 W m−2. The magnitude of the difference between original and improved methods was approximately 50% of the uncertainty among estimates by the world's global aerosol models reported by the IPCC-AR4 assessment report. Findings in the present study, therefore, may suggest that the model differences in the simplifications of the sulfur processes are still a part of the large uncertainty in their simulated radiative forcings.

  18. SULFATION OF PACHYMAN WITH CHLOROSULFONIC ACID USING THE IMPROVED WOLFROM METHOD

    Institute of Scientific and Technical Information of China (English)

    Qun Chen; Ai-yun Wang; Tian-tong Li; Cheng-fu Li; Qing-cai Jiao

    2006-01-01

    High purity polysaccharide of pachyman was isolated from the powder of Poria cocos sclerotium with an yield of 77.8%. The intrinsic viscosity of polysaccharide was found to be 78.95 mL/g in DMSO solution at 25℃. The isolated polysaccharide was reacted with chlorosulfonic acid to obtain pachyman sulfate using the improved Wolfrom method. The results of the orthogonality experiment on the sulfation reaction identified that the effectiveness of the reaction conditions on the degree of sulfation and the value of intrinsic viscosity is in the following order: molar ratio of chlorosulfonic acid to glucoside (3-5) > reaction temperature (60-80℃) > reaction time (1-2 h). The kinetic studies of the pachyman sulfationindicated that the hydrolysis is accompanied with the sulfation process. The decrease in intrinsic viscosity of the sulfated pachyman is proportional to the increase in the degree of sulfation under the mild reaction conditions of < 80℃,chlorosulfonic acid/glucoside mole ratio < 5, and reaction time < 2 h. Beyond the above reaction conditions, excessive loss of -OH group occurs during hydrolysis. The NMR results indicated a complete sulfation on C-6 and a partial sulfation on the C-2 and C-4 of glucoside.

  19. Elimination of sulfates from wastewaters by natural aluminosilicate modified with uric acid

    Directory of Open Access Journals (Sweden)

    J. De Los Santos

    2015-12-01

    Full Text Available Natural aluminosilicate activated by a heat/acid treatment, followed by modification with uric acid was used to remove sulfates for treatment of wastewater effluent. Natural aluminosilicates were studied in every stage of the modification (namely activation, modification with uric acid, and after sulfates absorption by scanning electron microscopy (SEM, spectroscopy X-ray diffraction (XRD, energy dispersive spectroscopy (EDS, surface area (BET, X-ray photoelectron spectroscopy (XPS, thermogravimetric analysis (TGA, and Z potential. More than 60% of the initial concentration of sulfates (500 mg/l was removed with the natural aluminosilicate modified with uric acid. Absorption isotherms rendered a mechanism with contributions from both Langmuir and Freundlich mechanisms. This study opens the path for the use of natural and abundant local material to remove sulfates using a modifier already present in wastewater effluents as contaminant.

  20. Isotopically exchangeable Al in coastal lowland acid sulfate soils

    Energy Technology Data Exchange (ETDEWEB)

    Yvanes-Giuliani, Yliane A.M. [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia); Centre Européen de Recherche et d' Enseignement des Géosciences de l' Environnement, Aix-Marseille Université, Aix en Provence (France); Fink, D. [Centre Européen de Recherche et d' Enseignement des Géosciences de l' Environnement, Aix-Marseille Université, Aix en Provence (France); Rose, J. [Institute for Environmental Research, Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Waite, T. David [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia); Collins, Richard N., E-mail: richard.collins@unsw.edu.au [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia)

    2016-01-15

    Periodic discharges of high concentrations of aluminium (Al) causing fish kills and other adverse effects occur worldwide in waterways affected by coastal lowland acid sulfate soils (CLASS). The exchangeability — a metal's ability to readily transfer between the soil solid- and solution-phases — of Al in these soils is therefore of particular importance as it has implications for metal transport, plant availability and toxicity to living organisms. In the present study, the concentrations of isotopically exchangeable Al (E values) were measured in 27 CLASS and compared with common salt extractions (i.e. KCl and CuCl{sub 2}) used to estimate exchangeable soil pools of Al. E values of Al were high in the soils, ranging from 357 to 3040 mg·kg{sup −1}. Exchangeable concentrations estimated using 1 M KCl were consistently lower than measured E values, although a reasonable correlation was obtained between the two values (E = 1.68 × Al{sub KCl}, r{sup 2} = 0.66, n = 25). The addition of a 0.2 M CuCl{sub 2} extraction step improved the 1:1 agreement between extractable and isotopically exchangeable Al concentrations, but lead to significant mobilisation of non-isotopically exchangeable Al in surficial ‘organic-rich’ CLASS having E values < 1000 mg·kg{sup −1}. It was concluded that currently used (i.e. 1 M KCl) methodology severely underestimates exchangeable Al and total actual acidity values in CLASS and should be corrected by a factor similar to the one determined here. - Highlights: • Isotopically exchangeable Al was compared to 1 M KCl or 0.2 M CuCl{sub 2} extractable Al. • 1 M KCl always underestimated isotopically exchangeable Al concentrations. • 0.2 M CuCl{sub 2} mobilised non-isotopically exchangeable Al • 1 M KCl values require correction of ~ 1.7 to reflect exchangeable Al concentrations.

  1. Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

    Institute of Scientific and Technical Information of China (English)

    邓立聪; 张亦飞; 陈芳芳; 曹绍涛; 游韶玮; 刘艳; 张懿

    2013-01-01

    The present work focused on the recycle of the sulfate and the metal ions from acidic wastewater dis-charged by nonferrous metallurgical industry. The effects of the temperature, the reactant concentration, the stirring speed and the metal ions on the reactive crystallization process of calcium sulfate between sulfuric acid and lime were systematically investigated. The morphology of the precipitated crystals evolved from platelet-like and nee-dle-like shape to rod-like shape when the temperature was increased from 25 to 70 °C. An increase in the agglom-eration of calcium sulfate was found with increasing lime concentration. Metal ions markedly retard the rate of crystallization of calcium sulfate dihydrate. The crystallization of gypsum was slowed with the existence of Mg2+in the solution, and the morphology of gypsum was transformed from platelet-like shape to rod-like shape when Mg2+concentration reached 0.08 mol·L-1. The amorphous ferric hydroxide was coated on the calcium sulfate after the co-precipitation process while Zn2+and Al3+ions in the solution enhanced the agglomeration of the calcium sulfate by absorbing on the surface of the crystals. Comprehensive acidic wastewater containing heavy metals was effi-ciently purified by the two stage lime neutralization technology, and highly agglomerated gypsum precipitates with needle-like shape were obtained. The precipitates could be purified by sulfuric acid washing, and the metal ions were effectively separated from the calcium sulfate by-products.

  2. Relationship between binding activity of sup 67 Ga and low sulfated acid glycosaminoglycans

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yasuhito; Tsukada, Fumitake; Kohno, Hiroyuki (Tohoku Coll. of Pharmacy, Sendai (Japan)); Kubodera, Akiko (Science Univ. of Tokyo (Japan). School of Pharmaceutical Sciences)

    1989-01-01

    Sulfate content of acid glycosaminoglycan (AGAG) extracted from granuloma which had been produced by turpentine oil was inversely proportional to the amount of {sub 67}Ga accumulation in the granuloma. Additionally, the lowest sulfation occurred in granuloma at a peak of inflammation when the uptake of {sub 67}Ga had reached a maximum. On the basis of electrophoretic pattern, sulfate content, and specific optical rotation, it was concluded that acid glycosaminoglycans obtained from granuloma are mainly composed of chondroitin sulfate-A, -B, and desulfated heparin, while haparan sulfate was a minor component. From in vitro assays, desulfated acid glycosaminoglycans, especially desulfated-heparin and desulfated-heparan sulfate, were found to have a high affinity to {sub 67}Ga. These results suggest that low- or de-sulfation of AGAG is related to the accumulation of {sub 67}Ga in inflammatory lesions such as granuloma. Moreover, these results suggest that {sub 67}Ga does not bind to glycosaminoglycans via sulfuric acid residues. (author).

  3. Homoserine as an Aspartic Acid Precursor for Synthesis of Proteoglycan Glycopeptide Containing Aspartic Acid and a Sulfated Glycan Chain.

    Science.gov (United States)

    Yang, Weizhun; Ramadan, Sherif; Yang, Bo; Yoshida, Keisuke; Huang, Xuefei

    2016-12-02

    Among many hurdles in synthesizing proteoglycan glycopeptides, one challenge is the incorporation of aspartic acid in the peptide backbone and acid sensitive O-sulfated glycan chains. To overcome this, a new strategy was developed utilizing homoserine as an aspartic acid precursor. The conversion of homoserine to aspartic acid in the glycopeptide was successfully accomplished by late stage oxidation using (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) and bis(acetoxy)iodobenzene (BAIB). This is the first time that a glycopeptide containing aspartic acid and an O-sulfated glycan was synthesized.

  4. Geophysical Fluid Dynamics Laboratory general circulation model investigation of the indirect radiative effects of anthropogenic sulfate aerosol

    Science.gov (United States)

    Ming, Yi; Ramaswamy, V.; Ginoux, Paul A.; Horowitz, Larry W.; Russell, Lynn M.

    2005-11-01

    The Geophysical Fluid Dynamics Laboratory (GFDL) atmosphere general circulation model, with its new cloud scheme, is employed to study the indirect radiative effect of anthropogenic sulfate aerosol during the industrial period. The preindustrial and present-day monthly mean aerosol climatologies are generated from running the Model for Ozone And Related chemical Tracers (MOZART) chemistry-transport model. The respective global annual mean sulfate burdens are 0.22 and 0.81 Tg S. Cloud droplet number concentrations are related to sulfate mass concentrations using an empirical relationship (Boucher and Lohmann, 1995). A distinction is made between "forcing" and flux change at the top of the atmosphere in this study. The simulations, performed with prescribed sea surface temperature, show that the first indirect "forcing" ("Twomey" effect) amounts to an annual mean of -1.5 W m-2, concentrated largely over the oceans in the Northern Hemisphere (NH). The annual mean flux change owing to the response of the model to the first indirect effect is -1.4 W m-2, similar to the annual mean forcing. However, the model's response causes a rearrangement of cloud distribution as well as changes in longwave flux (smaller than solar flux changes). There is thus a differing geographical nature of the radiation field than for the forcing even though the global means are similar. The second indirect effect, which is necessarily an estimate made in terms of the model's response, amounts to -0.9 W m-2, but the statistical significance of the simulated geographical distribution of this effect is relatively low owing to the model's natural variability. Both the first and second effects are approximately linearly additive, giving rise to a combined annual mean flux change of -2.3 W m-2, with the NH responsible for 77% of the total flux change. Statistically significant model responses are obtained for the zonal mean total indirect effect in the entire NH and in the Southern Hemisphere low

  5. Sulfate Mineral Formation from Acid-Weathered Phyllosilicates: Implications for the Aqueous History of Mars

    Science.gov (United States)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2015-01-01

    Phyllosilicates on Mars are thought to have formed under neutral to alkaline conditions during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Gya). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Gya). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the geologic and aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era may have been weathered by the prevailing acidic conditions that characterize the Hesperian. Therefore, the purpose of this study is to characterize the alteration products resulting from acid-sulfate weathered phyllosilicates in laboratory experiments. This study focuses on two phyllosilicates commonly identified with sulfates on Mars: nontronite and saponite. We also compare our results to observations of phyllosilicates and sulfates on Mars to better understand the formation process of sulfates in close proximity to phyllosilicates on Mars and constrain the aqueous conditions of these regions on Mars.

  6. Self-limited uptake of α-pinene-oxide to acidic aerosol: the effects of liquid-liquid phase separation and implications for the formation of secondary organic aerosol and organosulfates from epoxides

    Directory of Open Access Journals (Sweden)

    G. T. Drozd

    2013-03-01

    Full Text Available The reactive uptake of α-pinene oxide (αPO to acidic sulfate aerosol was studied under humid conditions in order to gain insight into the effects of liquid-liquid phase separation on aerosol heterogeneous chemistry and further elucidate the formation of secondary organic aerosol and organosulfates from epoxides. A continuous flow environmental chamber was used to monitor changes in diameter of monodisperse, deliquesced, acidic sulfate particles exposed to αPO at 30 and 50% RH. In order to induce phase separation and probe potential limits to particle growth from acidic uptake, αPO was introduced over a wide range of concentrations, from 200 ppb to 5 ppm. Uptake was observed to be highly dependent on initial aerosol pH. Significant uptake of αPO to aerosol was observed with initial pH Kp ranged from 0.2–1.6 × 10−4 m3 μg−1 and were correlated to initial particle acidity and particle organic content; particles with higher organic content had lower partition coefficients. Effective uptake coefficients (γ ranged from 0.4 to 4.7 × 10−5 and are much lower than recently reported for uptake to bulk solutions. In experiments in which αPO was added to bulk H2SO4 solutions, phase separation was observed for mass loadings similar to those observed with particles, and product distributions were dependent on acid concentration. Liquid-liquid phase separation in bulk experiments, along with our observations of decreased uptake to particles with the largest growth factors, suggest an organic coating forms upon uptake to particles, limiting reactive uptake.

  7. Sensitivity of high-spectral resolution and broadband thermal infrared nadir instruments to the chemical and microphysical properties of secondary sulfate aerosols in the upper-troposphere/lower-stratosphere

    Science.gov (United States)

    Sellitto, Pasquale; Legras, Bernard

    2016-04-01

    The observation of upper-tropospheric/lower-stratospheric (UTLS) secondary sulfate aerosols (SSA) and their chemical and microphysical properties from satellite nadir observations (with better spatial resolution than limb observations) is a fundamental tool to better understand their formation and evolution processes and then to estimate their impact on UTLS chemistry, and on regional and global radiative balance. Thermal infrared (TIR) observations are sensitive to the chemical composition of the aerosols due to the strong spectral variations of the imaginary part of the refractive index in this band and, correspondingly, of the absorption, as a function of the composition Then, these observations are, in principle, well adapted to detect and characterize UTLS SSA. Unfortunately, the exploitation of nadir TIR observations for sulfate aerosol layer monitoring is today very limited. Here we present a study aimed at the evaluation of the sensitivity of TIR satellite nadir observations to the chemical composition and the size distribution of idealised UTLS SSA layers. The sulfate aerosol particles are assumed as binary systems of sulfuric acid/water solution droplets, with varying sulphuric acid mixing ratios. The extinction properties of the SSA, for different sulfuric acid mixing ratios and temperatures, are systematically analysed. The extinction coefficients are derived by means of a Mie code, using refractive indices taken from the GEISA (Gestion et Étude des Informations Spectroscopiques Atmosphériques: Management and Study of Spectroscopic Information) spectroscopic database and log-normal size distributions with different effective radii and number concentrations. High-spectral resolution pseudo-observations are generated using forward radiative transfer calculations performed with the 4A (Automatized Atmospheric Absorption Atlas) radiative transfer model, to estimate the impact of the extinction of idealised aerosol layers, at typical UTLS conditions, on

  8. Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

    Energy Technology Data Exchange (ETDEWEB)

    Riva, Matthieu; Bell, David M.; Hansen, Anne-Maria Kaldal; Drozd, Greg T.; Zhang, Zhenfa; Gold, Avram; Imre, Dan; Surratt, Jason D.; Glasius, Marianne; Zelenyuk, Alla

    2016-06-07

    Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptake by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.

  9. Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols.

    Science.gov (United States)

    Riva, Matthieu; Bell, David M; Hansen, Anne-Maria Kaldal; Drozd, Greg T; Zhang, Zhenfa; Gold, Avram; Imre, Dan; Surratt, Jason D; Glasius, Marianne; Zelenyuk, Alla

    2016-06-07

    Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptake by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated with AP-derived SOA is lower compared to that of pure ABS particles, strongly dependent on particle composition, and therefore on particle size.

  10. Acid fog Deposition of Crusts on Basaltic Tephra Deposits in the Sand Wash Region of Kilauea Volcano: A Possible Mechanism for Siliceous-Sulfatic Crusts on Mars

    Science.gov (United States)

    Schiffman, P.; Zierenberg, R.; Marks, N.; Bishop, J. L.

    2004-12-01

    Although the presence of sulfate minerals in martian outcrops may imply the prior existence of standing bodies of surface water, in terrestrial volcanic settings, sulfatic alteration may also occur above the water table within the vadose zone. On the summit of Kilauea volcano, sulfur dioxide, which is continuously emitted from Halemaumau crater and rapidly sequestered into sulfuric acid-rich aerosol entrained in the prevailing trade winds, is subsequently precipitated as acid-fog immediately downwind from the caldera in the Kau Desert. The characteristic pH of surface tephra deposits is < 4.0 in Sand Wash, a region of continuous, acidic aerosol fall-out immediately SW of the caldera. The upper portion of the Keanakakoi Ash tephra in Sand Wash, deposited in the late 18th century, has a ubiquitous, 0.1-0.2 mm-thick coating of amorphous silica. Conversely, vertical walls of unconsolidated tephra, exposed within small, dry gullies eroded into the ca. 3-4 m-thick Keanakakoi section at Sand Wash, are coated with ca. 0.5-1.0 mm-thick, mixed amorphous silica and jarosite-bearing crusts. Since these crusts are denuded from their outcrops during ephemeral, but probably annual flooding events in Sand Wash, we believe that they must accumulate rapidly. These crusts are apparently formed via an evaporative mechanism whereby acidic pore fluids, circulating in the upper few m's within the highly porous tephra, are wicked towards the walls of the gullies. Geochemical modeling of the crust-forming process implies that the sulfate formation via evaporation occurs subsequent to minimal interaction of acidic pore fluids with the basaltic tephra. This also suggests that the cycle from acid-fog fall-out to precipitation of the siliceous-sulfatic crusts must occur quite rapidly. Production of siliceous-sulfatic crusts via acid-fog alteration may also be occurring on Mars. The occurrence of evaporitic sulfate and silica at Sand Wash in Kilauea may serve as an example of how the jarosite

  11. Dry powder aerosols generated by standardized entrainment tubes from drug blends with lactose monohydrate: 1. Albuterol sulfate and disodium cromoglycate.

    Science.gov (United States)

    Xu, Zhen; Mansour, Heidi M; Mulder, Tako; McLean, Richard; Langridge, John; Hickey, Anthony J

    2010-08-01

    The major objective of this study was: discriminatory assessment of dry powder aerosol performance using standardized entrainment tubes (SETs) and lactose-based formulations with two model drugs. Drug/lactose interactive physical mixtures (2%w/w) were prepared. Their properties were measured: solid-state characterization of phase behavior and molecular interactions by differential scanning calorimetry and X-ray powder diffraction; particle morphology and size by scanning electron microscopy and laser diffraction; aerosol generation by SETs and characterization by twin-stage liquid impinger and Andersen cascade impactor operated at 60 L/min. The fine particle fraction (FPF) was correlated with SET shear stress (tau(s)), using a novel powder aerosol deaggregation equation (PADE). Drug particles were <5 microm in volume diameter with narrow unimodal distribution (Span <1). The lowest shear SET (tau(s) = 0.624 N/m(2)) gave a higher emitted dose (ED approximately 84-93%) and lower FPF (FPF(6.4) approximately 7-25%). In contrast, the highest shear SET (tau(s) = 13.143 N/m(2)) gave a lower ED (ED approximately 75-89%) and higher FPF (FPF(6.4) approximately 15-46%). The performance of disodium cromoglycate was superior to albuterol sulfate at given tau(s), as was milled with respect to sieved lactose monohydrate. Excellent correlation was observed (R(2) approximately 0.9804-0.9998) when pulmonary drug particle release from the surface of lactose carriers was interpreted by PADE linear regression for dry powder formulation evaluation and performance prediction.

  12. Composition of Aerosols Over the Continential U.S.

    Science.gov (United States)

    1991-07-12

    term associated with sulfate. For ammonium sulfate D =4.5, for bisulfate D = 3.8, and D =1 for sulfuric acid . In order to estimate the organics via the... ammonium sulfate. Figure 16. The 3rd quarter aerosol constituents at each eastern location. The sulfate is assumed to be in the form of sulfuric acid , and...degree of neutralization by ammonium . The three common forms of particulate sulfate are ammonium sulfate ((NH4)2SO4), bisulfate (NH4 HSO4), and sulfuric

  13. Detailed predictive mapping of acid sulfate soil occurrence using electromagnetic induction data

    DEFF Research Database (Denmark)

    Beucher, Amélie; Boman, A; Mattbäck, S

    Acid sulfate soils are often called the nastiest soils in the world (Dent & Pons 1995). Releasing a toxic combination of acidity and metals into the recipient watercourses and estuaries, these soils represent a crucial environmental problem. Moreover, these soils can have a considerable economic...... impact through the resulting corrosion of concrete and steel infrastructures, or their poor geotechnical qualities. Therefore, mapping acid sulfate soil occurrence constitutes a key step to target the strategic areas for subsequent environmental risk management and mitigation. Conventional mapping (i.......e. soil sampling and subsequent pH measurements) has typically been used for acid sulfate soils. Nonetheless, spatial modelling techniques have recently been assessed, demonstrating promising results at catchment or regional extent (Beucher et al. 2014, 2015). Furthermore, electromagnetic induction data...

  14. Mapping potential acid sulfate soils in Denmark using legacy data and LiDAR-based derivatives

    DEFF Research Database (Denmark)

    Beucher, Amélie; Adhikari, Kabindra; Breuning-Madsen, H.

    2017-01-01

    Leaching large amounts of acidity and metals into recipient watercourses and estuaries, acid sulfate (a.s.) soils constitute a substantial environmental issue worldwide. Mapping of these soils enables measures to be taken to prevent pollution in high risk areas. In Denmark, legislation prohibits...

  15. Sulfur and nitrogen compounds in urban aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, R L

    1979-01-01

    This paper reports results from a detailed chemical and meteorological data base that has been accumulated for the New York City subregion. Aerosol sampling during August 1976 and February 1977 sampling periods was done only in an urban New York site and a background site at High Point, NJ. The sampling program was expanded to Brookhaven (Long Island) and New Haven, Connecticut sites during summer 1977 and winter 1978 sampling. Time resolution for aerosol filter samples was 6 hr, with some 3 hr sampling for the latter three periods. Parameters measured included chemical constituents: strong acid (quartz filters only), ammonium, sulfate and nitrate, sulfuric acid (limited data); physical parameters: aerosol size distributions by cascade impactor, cyclone sampler, EAA, on optical counter and a special diffusion battery-CNC apparatus; light scattering nephelometer and other instrumentation; chemically-speciated size classification by diffusion sampler; trace metals by atomic absorption; halogen compounds by NAA; meteorological measurements of RH, temperature, wind speed and direction; gaseous measurements of SO/sub 2/, ozone, NO/sub x/ and hydrocarbons at some locations for some sampling periods. The existence of aerosol sulfate in the ambient environment predominantly in the chemical form of sulfuric acid mostly neutralized by ammonia is now well documented. The average composition of fine particle (< 3.5 ..mu..m) sulfate in summer 1976 aerosols was approximately that letovicite ((NH/sub 4/)/sub 3/H(SO/sub 4/)/sub 2/). Based on the impactor data, about 85% of the aerosol sulfate mass was in the fine particle fraction. About 50% of this aerosol sulfate was deduced to be in the suboptical size regime (< 0.25 ..mu..m) from diffusion processor data. The H/sup +//SO/sub 4//sup 2 -/ ratio in suboptical aerosols did not significantly differ from that in fine fraction aerosol. The coarse particle sulfate was not associated with H/sup +/ or NH/sub 4//sup +/ and comprised

  16. Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

    Science.gov (United States)

    Zheng, Jun; Yang, Dongsen; Ma, Yan; Chen, Mindong; Cheng, Jin; Li, Shizheng; Wang, Ming

    2015-10-01

    A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3-) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3- ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4- signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3-ṡ(H2O)2 (m/z 97.014) and O-ṡH2OṡHNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm-3 gaseous H2SO4 and 0.5 μg m-3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.

  17. Radiative forcing estimates of sulfate aerosol in coupled climate-chemistry models with emphasis on the role of the temporal variability

    Directory of Open Access Journals (Sweden)

    C. Déandreis

    2012-06-01

    Full Text Available This paper describes the impact on the sulfate aerosol radiative effects of coupling the radiative code of a global circulation model with a chemistry-aerosol module. With this coupling, temporal variations of sulfate aerosol concentrations influence the estimate of aerosol radiative impacts. Effects of this coupling have been assessed on net fluxes, radiative forcing and temperature for the direct and first indirect effects of sulfate.

    The direct effect respond almost linearly to rapid changes in concentrations whereas the first indirect effect shows a strong non-linearity. In particular, sulfate temporal variability causes a modification of the short wave net fluxes at the top of the atmosphere of +0.24 and +0.22 W m−2 for the present and preindustrial periods, respectively. This change is small compared to the value of the net flux at the top of the atmosphere (about 240 W m−2. The effect is more important in regions with low-level clouds and intermediate sulfate aerosol concentrations (from 0.1 to 0.8 μg (SO4 m−3 in our model.

    The computation of the aerosol direct radiative forcing is quite straightforward and the temporal variability has little effect on its mean value. In contrast, quantifying the first indirect radiative forcing requires tackling technical issues first. We show that the preindustrial sulfate concentrations have to be calculated with the same meteorological trajectory used for computing the present ones. If this condition is not satisfied, it introduces an error on the estimation of the first indirect radiative forcing. Solutions are proposed to assess radiative forcing properly. In the reference method, the coupling between chemistry and climate results in a global average increase of 8% in the first indirect radiative forcing. This change reaches 50% in the most sensitive regions. However, the reference method is not suited to run long climate

  18. Algae as an electron donor promoting sulfate reduction for the bioremediation of acid rock drainage

    Energy Technology Data Exchange (ETDEWEB)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A., E-mail: jimfield@email.arizona.edu

    2016-11-05

    Highlights: • Algal biomass can serve as an electron donor to drive reduction of sulfate to sulfide. • Biogenic sulfide precipitates Cu{sup 2+} as stable sulfide mineral. • Cu{sup +2} removal in sulfidogenic bioreactors amended with algal biomass exceeded 99.5%. • Acidity in synthetic acid rock drainage was consumed by sulfate reduction. - Abstract: This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H{sub 2}SO{sub 4} and Cu{sup 2+}. Sulfate, sulfide, Cu{sup 2+} and pH were monitored throughout the experiment of 123 d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7 mg SO{sub 4}{sup 2−} d{sup −1}) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu{sup 2+} removal were observed in the endogenous control. In algae amended-columns, Cu{sup 2+} was precipitated with biogenic H{sub 2}S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry.

  19. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2012-05-01

    Full Text Available The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g. However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C. Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2 – which favour the heavy isotope, and

  20. Acidification of musts in warm regions with tartaric acid and calcium sulfate at industrial scale

    Directory of Open Access Journals (Sweden)

    Gómez Juan

    2015-01-01

    Full Text Available Acidification of musts is necessary in warm areas where high temperatures during ripening accelerate breathing com- bustion of tartaric acid and, in particular, malic acid in the berries. L(+ tartaric acid, L(- or D,L malic acid and lactic acids are the only chemical acidifiers authorized by the OIV and European Community regulations. The use of calcium sulfate (gypsum: CaSO4·2H2O is also authorized in the European Community as a complementary acidifier in generous and generous liquor 42 wines from Spain (a practice known as plastering, provided that the residual sulfate content in the wine does not exceed 2.5 g/L expressed as potassium sulfate. However, this practice is not yet approved by OIV. To predict the effect on pH of different acidi- fiers, several chemical modeling approaches have been described in the literature, in particular a simplified model where the acidity of wine is considered to be due to a monoprotic acid. The aim of this work is to verify this model at pilot and industrial scale in the acidification of musts with tartaric and calcium sulfate, added either individually and in combination, using doses up to 3 g/L and to study the modifications that these practices produce on the compositions of the resulting wines. This work sup- plies useful information to study this practice in OIV in order to consider its approval.

  1. Identifying sources of acidity and spatial distribution of acid sulfate soils in the Anglesea River catchment, southern Australia

    Science.gov (United States)

    Wong, Vanessa; Yau, Chin; Kennedy, David

    2015-04-01

    Globally, coastal and estuarine floodplains are frequently underlain by sulfidic sediments. When exposed to oxygen, sulfidic sediments oxidise to form acid sulfate soils, adversely impacting on floodplain health and adjacent aquatic ecoystems. In eastern Australia, our understanding of the formation of these coastal and estuarine floodplains, and hence, spatial distribution of acid sulfate soils, is relatively well established. These soils have largely formed as a result of sedimentation of coastal river valleys approximately 6000 years BP when sea levels were one to two metres higher. However, our understanding of the evolution of estuarine systems and acid sulfate soil formation, and hence, distribution, in southern Australia remains limited. The Anglesea River, in southern Australia, is subjected to frequent episodes of poor water quality and low pH resulting in closure of the river and, in extreme cases, large fish kill events. This region is heavily reliant on tourism and host to a number of iconic features, including the Great Ocean Road and Twelve Apostles. Poor water quality has been linked to acid leakage from mining activities and Tertiary-aged coal seams, peat swamps and acid sulfate soils in the region. However, our understanding of the sources of acidity and distribution of acid sulfate soils in this region remains poor. In this study, four sites on the Anglesea River floodplain were sampled, representative of the main vegetation communities. Peat swamps and intertidal marshes were both significant sources of acidity on the floodplain in the lower catchment. However, acid neutralising capacity provided by carbonate sands suggests that there are additional sources of acidity higher in the catchment. This pilot study has highlighted the complexity in the links between the floodplain, upper catchment and waterways with further research required to understand these links for targeted acid management strategies.

  2. Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

    Directory of Open Access Journals (Sweden)

    P. J. Gallimore

    2011-12-01

    Full Text Available Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent

  3. Production of fired construction brick from high sulfate-containing fly ash with boric acid addition.

    Science.gov (United States)

    Başpinar, M Serhat; Kahraman, Erhan; Görhan, Gökhan; Demir, Ismail

    2010-01-01

    The increase of power plant capacity has led to the production of an increasing amount of fly ash that causes high environmental impact in Turkey. Some of the fly ash is utilized within the fired brick industry but high sulfate-containing fly ash creates severe problems during sintering of the fired brick. This study attempted to investigate the potential for converting high sulfate-containing fly ash into useful material for the construction industry by the addition of boric acid. The chemical and mineralogical composition of fly ash and clay were investigated. Boric acid (H(3)BO(3)) was added to fly ash-clay mixtures with up to 5 wt.%. Six different series of test samples were produced by uniaxial pressing. The samples were fired at the industrial clay-brick firing temperatures of 800, 900 and 1000 degrees C. The microstructures of the fired samples were investigated by scanning electron microscopy and some physical and mechanical properties were measured. It was concluded that the firing at conventional brick firing temperature of high sulfate fly ash without any addition of boric acid resulted in very weak strength bricks. The addition of boric acid and clay simultaneously to the high sulfate- containing fly ash brick dramatically increased the compressive strength of the samples at a firing temperature of 1000 degrees C by modifying the sintering behaviour of high sulfate fly ash.

  4. Effects of inhaled acid aerosols on lung mechanics: an analysis of human exposure studies.

    Science.gov (United States)

    Utell, M J

    1985-11-01

    There exist significant gaps in our understanding of human health effects from inhalation of pollutants associated with acid precipitation. Controlled clinical studies examine effects of criteria pollutants almost exclusively by assessing changes in lung mechanics. One constituent of acid precipitation, sulfuric acid aerosols, has been shown to induce bronchoconstriction in exercising extrinsic asthmatics at near ambient levels. These asthmatics may be an order of magnitude more sensitive to sulfuric acid aerosols than normal adults. More recently, a second component nitrogen dioxide has been observed to provoke changes in lung mechanics at progressively lower concentrations. To date, virtually no data exist from clinical exposures to acidic aerosols for subjects with chronic obstructive pulmonary disease.

  5. Acid Sulfate Weathering on Mars: Results from the Mars Exploration Rover Mission

    Science.gov (United States)

    Ming, Douglas W.; Morris, R. V.; Golden, D. C.

    2006-01-01

    Sulfur has played a major role in the formation and alteration of outcrops, rocks, and soils at the Mars Exploration Rover landing sites on Meridiani Planum and in Gusev crater. Jarosite, hematite, and evaporite sulfates (e.g., Mg and Ca sulfates) occur along with siliciclastic sediments in outcrops at Meridiani Planum. The occurrence of jarosite is a strong indicator for an acid sulfate weathering environment at Meridiani Planum. Some outcrops and rocks in the Columbia Hills in Gusev crater appear to be extensively altered as suggested by their relative softness as compared to crater floor basalts, high Fe(3+)/FeT, iron mineralogy dominated by nanophase Fe(3+) oxides, hematite and/or goethite, corundum-normative mineralogies, and the presence of Mg- and Casulfates. One scenario for aqueous alteration of these rocks and outcrops is that vapors and/or fluids rich in SO2 (volcanic source) and water interacted with rocks that were basaltic in bulk composition. Ferric-, Mg-, and Ca-sulfates, phosphates, and amorphous Si occur in several high albedo soils disturbed by the rover's wheels in the Columbia Hills. The mineralogy of these materials suggests the movement of liquid water within the host material and the subsequent evaporation of solutions rich in Fe, Mg, Ca, S, P, and Si. The presence of ferric sulfates suggests that these phases precipitated from highly oxidized, low-pH solutions. Several hypotheses that invoke acid sulfate weathering environments have been suggested for the aqueous formation of sulfate-bearing phases on the surface of Mars including (1) the oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials by solutions enriched by volcanic gases (e.g., SO2); and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials.

  6. Stabilization of human prostatic acid phosphatase by coupling with chondroitin sulfate.

    Science.gov (United States)

    Luchter-Wasylewska, E; Dulińska, J; Ostrowski, W S; Torchilin, V P; Trubetskoy, V S

    1991-02-01

    Human prostatic acid phosphatase (PAP) (EC 3.1.3.2) was covalently linked to chondroitin sulfate A from whale cartilage. In order to bind the protein amino groups with the preactivated carboxyl groups of chondroitin sulfate, 1-ethyl-3-(3'-dimethylaminepropyl)carbodiimide and N-hydroxysulfosuccinimide were used as coupling agents. The product was soluble and enzymatically active. The activity was on average 25% higher than that of the free enzyme. The product was heterogeneous in respect to charge and Mr (50-1500) kDa, as determined by chromatography on Sephacryl S 300 and polyacrylamide gel electrophoresis. The resulting polymers contained covalently bound chondroitin sulfate, as shown by the biotin-avidin test. The modified enzyme is more resistant against various denaturing agents, e.g., urea, ethanol, and heat. Thus covalent modification of PAP by cross-linking to chondroitin sulfate could be the preferred method for stabilization of its biological activity.

  7. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    Science.gov (United States)

    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.

  8. The NH4--NO3--Cl--SO42--H2O Aerosol System and its Gas Phase Precursors at a Rural Site in the Amazon Basin: How Relevant are Mineral Cations and Soluble Organic Acids?

    Science.gov (United States)

    Helas, G.; Trebs, I.; Metzger, S.; Meixner, F. X.; Hoffer, A.; Moura, M. A.; da Silva, R. S.; Rudich, Y.; Falkovich, A.; Artaxo, P.; Slanina, J.; Andreae, M. O.

    2004-12-01

    We performed real-time measurements of ammonia (NH3), nitric acid (HNO3), hydrochloric acid (HCl), sulfur dioxide (SO2) and the water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), chloride (Cl-), and sulfate (SO42-) at a pasture site in the Amazon Basin (Rondônia, Brazil). The measurements were made during the closing of the dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions) (12 Sep. to 14 Nov. 2002, LBA-SMOCC*), using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC). Real-time data were combined with measurements of mineral cations (K+ , Ca2+ , Mg2+) and low-molecular weight (LMW) polar organic acids on 12-, 24- and 48-hours integrated filter samples. The contribution of inorganic species to the fine particulate mass (Dp 90 %) NH4NO3 and NH4Cl were predicted to be formed in the aqueous aerosol phase. Cl- was largely driven out of the aerosol phase by reaction of KCl with HNO3 and H2SO4. As shown by an updated version of EQSAM, which incorporates mineral aerosol species and lumped LMW polar organic acids, daytime aerosol NH4+ was mainly balanced by organic compounds. *Large Scale Biosphere Atmosphere Experiment in Amazonia Smoke Aerosols, Clouds, Rainfall and Climate: Aerosols from Biomass Burning Perturb Global and Regional Climate).

  9. Efflorescent sulfates from Baia Sprie mining area (Romania) — Acid mine drainage and climatological approach

    Energy Technology Data Exchange (ETDEWEB)

    Buzatu, Andrei, E-mail: andrei.buzatu@uaic.ro [“Alexandru Ioan Cuza” University of Iaşi, Department of Geology, 20A Carol I Blv., 700505 Iaşi (Romania); Dill, Harald G. [Gottfried Wilhelm Leibniz University, Welfengarten 1 D-30167, Hannover (Germany); Buzgar, Nicolae [“Alexandru Ioan Cuza” University of Iaşi, Department of Geology, 20A Carol I Blv., 700505 Iaşi (Romania); Damian, Gheorghe [Technical University Cluj Napoca, North University Center of Baia Mare, 62A Dr. Victor Babeş Street, 430083 Baia Mare (Romania); Maftei, Andreea Elena; Apopei, Andrei Ionuț [“Alexandru Ioan Cuza” University of Iaşi, Department of Geology, 20A Carol I Blv., 700505 Iaşi (Romania)

    2016-01-15

    The Baia Sprie epithermal system, a well-known deposit for its impressive mineralogical associations, shows the proper conditions for acid mine drainage and can be considered a general example for affected mining areas around the globe. Efflorescent samples from the abandoned open pit Minei Hill have been analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and near-infrared (NIR) spectrometry. The identified phases represent mostly iron sulfates with different hydration degrees (szomolnokite, rozenite, melanterite, coquimbite, ferricopiapite), Zn and Al sulfates (gunningite, alunogen, halotrichite). The samples were heated at different temperatures in order to establish the phase transformations among the studied sulfates. The dehydration temperatures and intermediate phases upon decomposition were successfully identified for each of mineral phases. Gunningite was the single sulfate that showed no transformations during the heating experiment. All the other sulfates started to dehydrate within the 30–90 °C temperature range. The acid mine drainage is the main cause for sulfates formation, triggered by pyrite oxidation as the major source for the abundant iron sulfates. Based on the dehydration temperatures, the climatological interpretation indicated that melanterite formation and long-term presence is related to continental and temperate climates. Coquimbite and rozenite are attributed also to the dry arid/semi-arid areas, in addition to the above mentioned ones. The more stable sulfates, alunogen, halotrichite, szomolnokite, ferricopiapite and gunningite, can form and persists in all climate regimes, from dry continental to even tropical humid. - Highlights: • Efflorescent salts from mining areas have a great impact on the environment. • Secondary minerals are influenced by geology, hydrology, biology and climate. • AMD-precipitates samples were analyzed by XRD, SEM, Raman and NIR spectrometry. • The dehydration temperatures

  10. Constraining the long-term climate reponse to stratospheric sulfate aerosols injection by the short-term volcanic climate response

    Science.gov (United States)

    Plazzotta, M.; Seferian, R.; Douville, H.; Kravitz, B.; Tilmes, S.; Tjiputra, J.

    2016-12-01

    Rising greenhouse gas emissions are leading to global warming and climate change, which will have multiple impacts on human society. Geoengineering methods like solar radiation management by stratospheric sulfate aerosols injection (SSA-SRM) aim at treating the symptoms of climate change by reducing the global temperature. Since a real-world testing cannot be implemented, Earth System Models (ESMs) are useful tools to assess the climate impacts of such geoengineering methods. However, coordinated simulations performed with the Geoengineering Model Intercomparison Project (GeoMIP) have shown that climate cooling in response to a continuous injection of 5Tg of SO2 per year under RCP45 future projection (the so-called G4 experiment) differs substantially between ESMs. Here, we employ a volcano analog approach to constrain the climate response in SSA-SRM geoengineering simulations across an ensemble of 10 ESMs. We identify an emergent relationship between the long-term cooling in responses to the mitigation of the clear-sky surface downwelling shortwave radiation (RSDSCS), and the short-term cooling related to the change in RSDSCS during the major tropical volcanic eruptions observed over the historical period (1850-2005). This relationship explains almost 80% of the multi-model spread. Combined with contemporary observations of the latest volcanic eruptions (satellite observations and model reanalyzes), this relationship provides a tight constraint on the climate impacts of SSA-SRM. We estimate that a continuous injection of SO2 aerosols into the stratosphere will reduce the global average temperature of continental land surface by 0.47 K per W m-2, impacting both hydrological and carbon cycles. Compared with the unconstrained ESMs ensemble (range from 0.32 to 0.92 K per W m-2 ), our estimate represents much higher confidence ways to assess the impacts of SSA-SRM on the climate while ruling the most extreme projections of the unconstrained ensemble extremely unlikely.

  11. A study of uncertainties in the sulfate distribution and its radiative forcing associated with sulfur chemistry in a global aerosol model

    Directory of Open Access Journals (Sweden)

    D. Goto

    2011-11-01

    Full Text Available The direct radiative forcing by sulfate aerosols is still uncertain, mainly because the uncertainties are largely derived from differences in sulfate column burdens and its vertical distributions among global aerosol models. One possible reason for the large difference in the computed values is that the radiative forcing delicately depends on various simplifications of the sulfur processes made in the models. In this study, therefore, we investigated impacts of different parts of the sulfur chemistry module in a global aerosol model, SPRINTARS, on the sulfate distribution and its radiative forcing. Important studies were effects of simplified and more physical-based sulfur processes in terms of treatment of sulfur chemistry, oxidant chemistry, and dry deposition process of sulfur components. The results showed that the difference in the aqueous-phase sulfur chemistry among these treatments has the largest impact on the sulfate distribution. Introduction of all the improvements mentioned above brought the model values noticeably closer to in-situ measurements than those in the simplified methods used in the original SPRINTARS model. At the same time, these improvements also brought the computed sulfate column burdens and its vertical distributions into good agreement with other AEROCOM model values. The global annual mean radiative forcing due to the direct effect of anthropogenic sulfate aerosol was thus estimated to be −0.26 W m−2 (−0.30 W m−2 with a different SO2 inventory, whereas the original SPRINTARS model showed −0.18 W m−2 (−0.21 W m−2 with a different SO2 inventory. The magnitude of the difference between original and improved methods was approximately 50% of the uncertainty among estimates by the world's global aerosol models reported by the IPCC-AR4 assessment report. Findings in the present study, therefore, may suggest that the model differences in the

  12. Microbial sulfate reduction under sequentially acidic conditions in an upflow anaerobic packed bed bioreactor

    Energy Technology Data Exchange (ETDEWEB)

    Jong, T.; Parry, D.L. [Charles Darwin University, Darwin, NT (Australia). Faculty for Educational Health & Science

    2006-07-15

    The aim of this study was to operate an upflow anaerobic packed bed reactor (UAPB) containing sulfate reducing bacteria (SRB) under acidic conditions similar to those found in acid mine drainage (AMD). The UAPB was filled with sand and operated under continuous flow at progressively lower pH and was shown to be capable of supporting sulfate reduction at pH values of 6.0, 5.0, 4.5, 4.0 and 3.5 in a synthetic medium containing 53.5 mmol l{sup -1} lactate. Sulfate reduction rates of 553-1052 mmol m{sup -3} d{sup -1} were obtained when the influent solution pH was progressively lowered from pH 6.0 to 4.0, under an optimal flow rate of 2.61 ml min{sup -1}. When the influent pH was further lowered to pH 3.5, sulfate reduction was substantially reduced with only about 1% sulfate removed at a rate of 3.35 mmol m{sup -3} d{sup -1} after 20 days of operation. However, viable SRB were recovered from the column, indicating that the SRB population was capable of surviving and metabolizing at low levels even at pH 3.5 conditions for at least 20 days. The changes in conductivity in the SRB column did not always occur with changes in pH and redox potential, suggesting that conductivity measurements may be more sensitive to SRB activity and could be used as an additional tool for monitoring SRB activity. The bioreactor containing SRB was able to reduce sulfate and generate alkalinity even when challenged with influent as low as pH 3.5, indicating that such treatment systems have potential for bioremediating highly acidic, sulfate contaminated waste waters.

  13. Low molecular weight organic acids in aerosol particles from Rondônia, Brazil, during the biomass-burning, transition and wet periods

    Directory of Open Access Journals (Sweden)

    A. H. Falkovich

    2005-01-01

    Full Text Available Particles from biomass burning and regional haze were sampled in Rondônia, Brazil, during dry, transition and wet periods from September to November 2002, as part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate field campaign. Water soluble organic and inorganic compounds in bulk (High Volume and Stacked Filter Unit sampler and size-resolved (Micro Orifice Uniform Deposit Impactor – MOUDI smoke samples were determined by ion chromatography. It was found that low molecular weight polar organic acids account for a significant fraction of the water soluble organic carbon (WSOC in biomass burning aerosols (C2-C6 dicarboxylic acids reached up to 3.7% and one-ring aromatic acids reached up to 2% of fine fraction WSOC during burning period. Short dicarboxylic (C2-C6 acids are dominated by oxalic acid followed by malonic and succinic acids. The largest ionic species is ammonium sulfate (60–70% of ionic mass. It was found that most of the ionic mass is concentrated in submicrometer-sized particles. Based on the size distribution and correlations with K+, a known biomass burning tracer, it is suggested that many of the organic acids are directly emitted by vegetation fires. Concentrations of dicarboxylic acids in the front and back filters of high volume sampler were determined. Based on these measurements, it was concluded that in the neutral or slightly basic smoke particles typical of this region, dicarboxylic acids are mostly confined to the particulate phase. Finally, it is shown that the distribution of water soluble species shifts to larger aerosols sizes as the aerosol population ages and mixes with other aerosol types in the atmosphere.

  14. Algae as an electron donor promoting sulfate reduction for the bioremediation of acid rock drainage.

    Science.gov (United States)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A

    2016-11-05

    This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H2SO4 and Cu(2+). Sulfate, sulfide, Cu(2+) and pH were monitored throughout the experiment of 123d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7mg SO4(2-) d(-1)) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu(2+) removal were observed in the endogenous control. In algae amended-columns, Cu(2+) was precipitated with biogenic H2S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry.

  15. Effects of NO{sub x} and SO{sub 2} injections by supersonic aviation on sulfate aerosol and ozone in the troposphere and stratosphere

    Energy Technology Data Exchange (ETDEWEB)

    Dyominov, I.G.; Zadorozhny, A.M. [Novosibirsk State Univ. (Russian Federation); Elansky, N.F. [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Atmospheric Physics

    1997-12-31

    The impact of supersonic aviation on atmospheric ozone and sulfate aerosol is examined with the help of a two-dimensional dynamical/radiative/chemical model of ozonosphere including aerosol physics. For SO{sub 2} emissions from aircraft as gas, gas/particles (90%/10%) mix, and particles of 0.01 {mu}m radius the sulphate aerosol surface density at maximum of changes increases against its background value by {approx}50%, {approx}75%, and {approx}200%, respectively. This effect of SO{sub 2} emissions with insignificant NO{sub x} injection leads to a significant decrease of total ozone by 2015 in the entire atmosphere. For NO{sub x} emissions which are anticipated in future (EI(NO{sub x}) = 15) any kind of SO{sub 2} emission results in significant weakening of supersonic aviation impact on ozone layer in the Northern Hemisphere. (author) 14 refs.

  16. Acid sulfate soils and human health--a Millennium Ecosystem Assessment.

    Science.gov (United States)

    Ljung, Karin; Maley, Fiona; Cook, Angus; Weinstein, Philip

    2009-11-01

    Acid sulfate soils have been described as the "nastiest soils on earth" because of their strong acidity, increased mobility of potentially toxic elements and limited bioavailability of nutrients. They only cover a small area of the world's total problem soils, but often have significant adverse effects on agriculture, aquaculture and the environment on a local scale. Their location often coincides with high population density areas along the coasts of many developing countries. As a result, their negative impacts on ecosystems can have serious implications to those least equipped for coping with the low crop yields and reduced water quality that can result from acid sulfate soil disturbance. The Millennium Ecosystem Assessment called on by the United Nations in 2000 emphasised the importance of ecosystems for human health and well-being. These include the service they provide as sources of food and water, through the control of pollution and disease, as well as for the cultural services ecosystems provide. While the problems related to agriculture, aquaculture and the environment have been the focus of many acid sulfate soil management efforts, the connection to human health has largely been ignored. This paper presents the potential health issues of acid sulfate soils, in relation to the ecosystem services identified in the Millennium Ecosystem Assessment. It is recognised that significant implications on food security and livelihood can result, as well as on community cohesiveness and the spread of vector-borne disease. However, the connection between these outcomes and acid sulfate soils is often not obvious and it is therefore argued that the impact of such soils on human well-being needs to be recognised in order to raise awareness among the public and decision makers, to in turn facilitate proper management and avoid potential human ill-health.

  17. Desulfosporosinus acididurans sp. nov.: an acidophilic sulfate-reducing bacterium isolated from acidic sediments

    NARCIS (Netherlands)

    Sanchez Andrea, I.; Stams, A.J.M.; Hedrich, S.; Nancucheo, I.; Johnson, D.B.

    2015-01-01

    Three strains of sulfate-reducing bacteria (M1T, D, and E) were isolated from acidic sediments (White river and Tinto river) and characterized phylogenetically and physiologically. All three strains were obligately anaerobic, mesophilic, spore-forming straight rods, stained Gram-negative and

  18. BILE SECRETION OF SULFATED GLYCOLITHOCHOLIC ACID IS REQUIRED FOR ITS CHOLESTATIC ACTION IN RATS

    NARCIS (Netherlands)

    KUIPERS, F; HARDONK, MJ; VONK, RJ; VANDERMEER, R

    1992-01-01

    To test our hypothesis that the cholestatic action of sulfated glycolithocholic acid (SGLC) in the rat is related to its interaction with calcium in the biliary tree [R. van der Meer, R. J. Vonk, and F. Kuipers. Am. J. Physiol. 254 (Gastrointest. Liver Physiol. 17): G644-G649, 1988], we have now com

  19. Low molecular weight organic acids in aerosol particles from Rondônia, Brazil, during the biomass-burning, transition and wet periods

    Directory of Open Access Journals (Sweden)

    P. Artaxo

    2004-10-01

    Full Text Available Particles from biomass burning and regional haze were sampled in Rondônia, Brazil, during dry, transition and wet periods from September to November 2002, as part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate field campaign. Water soluble organic and inorganic compounds in bulk (High Volume and Stacked Filter Unit sampler and size-resolved (Micro Orifice Uniform Deposit Impactor – MOUDI smoke samples were determined by ion chromatography. It was found that low molecular weight polar organic acids account for a significant fraction of the water soluble organic carbon (WSOC in biomass burning aerosols (C2-C6 dicarboxylic acids reached up to 3.7% and one-ring aromatic acids reached up to 2% of fine fraction WSOC during burning period. Short dicarboxylic (C2-C6 acids are dominated by oxalic acid followed by malonic and succinic acids. The largest ionic species is ammonium sulfate (60–70% of ionic mass. It was found that most of the ionic mass is concentrated in submicrometer-sized particles. Based on the size distribution and correlations with K+, a known biomass burning tracer, it is suggested that many of the organic acids are directly emitted by vegetation fires. It is concluded that the dicarboxylic acids are mostly confined to the particulate phase, and no evidence for semi-volatile behavior was observed. Finally, it is shown that the distribution of water soluble species shifts to larger aerosols sizes as the aerosol population ages and mixes with other aerosol types in the atmosphere.

  20. Zinc-Nickel Codeposition in Sulfate Solution Combined Effect of Cadmium and Boric Acid

    Directory of Open Access Journals (Sweden)

    Y. Addi

    2011-01-01

    Full Text Available The combined effect of cadmium and boric acid on the electrodeposition of zinc-nickel from a sulfate has been investigated. The presence of cadmium ion decreases zinc in the deposit. In solution, cadmium inhibits the zinc ion deposition and suppresses it when deposition potential value is more negative than −1.2 V. Low concentration of CdSO4 reduces the anomalous nature of Zn-Ni deposit. Boric acid decreases current density and shifts potential discharge of nickel and hydrogen to more negative potential. The combination of boric acid and cadmium increases the percentage of nickel in the deposit. Boric acid and cadmium.

  1. Treatment of acid mine drainage by sulfate reducing bacteria with iron in bench scale runs.

    Science.gov (United States)

    Bai, He; Kang, Yong; Quan, Hongen; Han, Yang; Sun, Jiao; Feng, Ying

    2013-01-01

    In order to treat acid mine drainage (AMD) effectively using sulfate-reducing bacteria (SRB) at high concentration of sulfate and heavy metals, Fe(0) was added to enhance the activity of SRB. When AMD was treated by SRB and Fe(0) at 25 °C, more than 61% of sulfate was removed and the effluent pH was improved from 2.75 to 6.20 during the operation. Cu(2+) was removed effectively with the removal efficiency at 99%, while only 86% of Fe(2+) was removed during the AMD treatment, without conspicuous change of Mn(2+) in the effluent in the process. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Vacuum FTIR observation on hygroscopic properties and phase transition of malonic acid aerosols

    Science.gov (United States)

    Shao, Xu; Zhang, Yun; Pang, Shu-Feng; Zhang, Yun-Hong

    2017-02-01

    A novel approach based on a combination of a pulse relative humidity (RH) controlling system and a rapid scan vacuum FTIR spectrometer was utilized to investigate the hygroscopic property and phase transition of malonic acid (MA) aerosols. By using this approach, both water vapor amount around the aerosols and water content within aerosols with sub-second time resolution were obtained. Based on the features of FTIR absorbing bands, it can be known that the evolution of hydrogen-bonding structures of malonic acid aerosols took place from (H2O)n-MA to MA-MA accompanying with phase transition in the dehumidifying process. And in present paper, the stepwise efflorescence of MA aerosols and nucleation rates at different RHs are first reported. Our observation has shown that the efflorescence of MA started at ∼17% RH and the nucleation rates increased with decreasing RH.

  3. Volatile fatty acids as substrates for iron and sulfate reduction in Arctic marine sediments, Svalbard

    Science.gov (United States)

    Finke, N.; Vandieken, V.; Jorgensen, B. B.

    2006-12-01

    Anaerobic degradation of complex organic material in aquatic systems is a multi-step process. The metabolic products of fermentative bacteria serve as electron donors for the terminal oxidizing bacteria. In marine sediments, iron reduction and sulfate reduction are generally the most important terminal oxidation processes in the upper anoxic zone [1]. Microorganisms that reduce iron and sulfate may use a broad range of electron donors, yet the list of potential substrates provides little information about the substrates used in situ by these organisms. Investigations on the electron donors for sulfate reducers in marine sediments have shown that volatile fatty acids (VFA), and in particular acetate, together with hydrogen are the major substrates (e.g. [2-4]). Similar investigations for iron reduction or simultaneous iron and sulfate reduction are lacking for marine sediments. Furthermore, most of these studies were made in temperate sediments and little is known about the substrates for sulfate reducers in permanently cold sediments, which account for >90% of the ocean floor [5]. We investigated the relative contributions of iron reduction and sulfate reduction to the terminal oxidation of organic carbon and the importance of acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in permanently cold, Arctic sediments from Svalbard. In the surface layer (0-2 cm) sulfate reduction accounted for 2/3 of the organic carbon oxidation (determined as DIC production), the remaining 1/3 were attributed to iron reduction. In the 5-9 cm layer sulfate reduction was the sole important terminal oxidation step. The contribution of acetate to terminal oxidation was determined by radiotracer incubation as well as from the accumulation after the inhibition of sulfate reduction by selenate. The rates determined with the two methods varied by less than 20%. Acetate turnover, determined with the tracer incubations, accounted for 10 and 40% of

  4. Phase transitions and hygroscopic growth of aerosol particles containing humic acid and mixtures of humic acid and ammonium sulphate

    Directory of Open Access Journals (Sweden)

    C. L. Badger

    2006-01-01

    Full Text Available The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR spectroscopy and tandem differential mobility analysis (TDMA. A growth factor of 1.16 at 85% relative humidity (RH was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidities with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH and increases the efflorescence relative humidity (ERH of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the single-component aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently.

  5. Sulfated diesters of okadaic acid and DTX-1: Self-protective precursors of diarrhetic shellfish poisoning (DSP) toxins.

    Science.gov (United States)

    Hu, Tingmo; LeBlanc, Patricia; Burton, Ian W; Walter, John A; McCarron, Pearse; Melanson, Jeremy E; Strangman, Wendy K; Wright, Jeffrey L C

    2017-03-01

    Many toxic secondary metabolites used for defense are also toxic to the producing organism. One important way to circumvent toxicity is to store the toxin as an inactive precursor. Several sulfated diesters of the diarrhetic shellfish poisoning (DSP) toxin okadaic acid have been reported from cultures of various dinoflagellate species belonging to the genus Prorocentrum. It has been proposed that these sulfated diesters are a means of toxin storage within the dinoflagellate cell, and that a putative enzyme mediated two-step hydrolysis of sulfated diesters such as DTX-4 and DTX-5 initially leads to the formation of diol esters and ultimately to the release of free okadaic acid. However, only one diol ester and no sulfated diesters of DTX-1, a closely related DSP toxin, have been isolated leading some to speculate that this toxin is not stored as a sulfated diester and is processed by some other means. DSP components in organic extracts of two large scale Prorocentrum lima laboratory cultures have been investigated. In addition to the usual suite of okadaic acid esters, as well as the free acids okadaic acid and DTX-1, a group of corresponding diol- and sulfated diesters of both okadaic acid and DTX-1 have now been isolated and structurally characterized, confirming that both okadaic acid and DTX-1 are initially formed in the dinoflagellate cell as the non-toxic sulfated diesters. Copyright © 2017. Published by Elsevier B.V.

  6. Determination of sulfate in the wet-process of phosphoric acid by reverse flow injection

    Directory of Open Access Journals (Sweden)

    Wenhui Shi

    2014-01-01

    Full Text Available An improved method based on reverse flow injection is proposed for determining sulfate concentration in the wet-process of phosphoric acid (WPA. The effect of reagent composition, flow rate, temperature, acid concentration, length of the reaction coil, and linear response range on the flow system is discussed in detail. Optimal conditions are established for determining sulfate in the WPA samples. Baseline drift is avoided by a periodic washing step with EDTA in an alkaline medium. A linear response is observed within a range of 20 - 360 mg L-1, given by the equation A = 0.0020C (mg L-1 + 0.0300, R² = 0.9991. The detection limit of the proposed method for sulfate analysis is 3 mg L-1, and the relative standard deviation (n = 12 of sulfate absorbance peak is less than 1.60%. This method has a rate of up to 29 samples per hour, and the results compare well with those obtained with gravimetric method.

  7. Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

    2011-05-24

    A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

  8. Metal complexation inhibits the effect of oxalic acid in aerosols as cloud condensation nuclei (CCN

    Directory of Open Access Journals (Sweden)

    T. Furukawa

    2010-11-01

    Full Text Available Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to cancel the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA play a key role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is one of the major components of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca and zinc (Zn in aerosols collected at Tsukuba in Japan with fractionation based on particle size using an impactor aerosol sampler. It was shown that 10–60% and 20–100% of the total Ca and Zn in the finer particles (<2.1 μm were present as Ca and Zn oxalate complexes, respectively. Oxalic acid can act as CCN because of its hygroscopic properties, while metal complexes are not hygroscopic, and so cannot be CCN. Based on the concentration of noncomplexed and metal-complexed oxalate species, we found that most of the oxalic acid is present as metal oxalate complexes in the aerosols, suggesting that oxalic acid does not act as CCN in the atmosphere. Similar results are expected for other dicarboxylic acids, such as malonic and succinic acids. Thus, it is possible that the cooling effect of organic aerosols assumed in various climate modeling studies is overestimated because of the lack of information on metal oxalate complexes in aerosols.

  9. Improved process for the production of cellulose sulfate using sulfuric acid/ethanol solution.

    Science.gov (United States)

    Chen, Guo; Zhang, Bin; Zhao, Jun; Chen, Hongwen

    2013-06-05

    An improved process for production of cellulose sulfate (CS) was developed by using sulfuric acid/ethanol solution as sulfonating agent and Na2SO4 as water absorbent. The FTIR, SEM and TG analysis were used to characterize the CS prepared. The total degree of substitution and viscosity of the product solution (2%, w/v) were ranging from 0.28 to 0.77 and from 115 to 907 mPa s, respectively, by changing the process parameters such as the amount of Na2SO4, the reaction time, the temperature, the sulfuric acid/alcohol ratio and liquid/solid ratio. The results indicated that the product with DS (0.28-0.77) and η2% (115-907) mPa s could be produced by using this improved process and more cellulose sulfate could be produced when cellulose was sulfonated for 3-4 h at -2 °C in sulfuric acid/ethanol (1.4-1.6) solution with addition of 0.8 g Na2SO4. The (13)C NMR indicated that the sulfate group of CS produced using sulfuric acid/ethanol solution was at C6 position.

  10. Hexuronic acid stereochemistry determination in chondroitin sulfate glycosaminoglycan oligosaccharides by electron detachment dissociation.

    Science.gov (United States)

    Leach, Franklin E; Ly, Mellisa; Laremore, Tatiana N; Wolff, Jeremy J; Perlow, Jacob; Linhardt, Robert J; Amster, I Jonathan

    2012-09-01

    Electron detachment dissociation (EDD) has previously provided stereo-specific product ions that allow for the assignment of the acidic C-5stereochemistry in heparan sulfate glycosaminoglycans (GAGs), but application of the same methodology to an epimer pair in the chondroitin sulfate glycoform class does not provide the same result. A series of experiments have been conducted in which glycosaminoglycan precursor ions are independently activated by electron detachment dissociation (EDD), electron induced dissociation (EID), and negative electron transfer dissociation (NETD) to assign the stereochemistry in chondroitin sulfate (CS) epimers and investigate the mechanisms for product ion formation during EDD in CS glycoforms. This approach allows for the assignment of electronic excitation products formed by EID and detachment products to radical pathways in NETD, both of which occur simultaneously during EDD. The uronic acid stereochemistry in electron detachment spectra produces intensity differences when assigned glycosidic and cross-ring cleavages are compared. The variations in the intensities of the doubly deprotonated (0,2)X(3) and Y(3) ions have been shown to be indicative of CS-A/DS composition during the CID of binary mixtures. These ions can provide insight into the uronic acid composition of binary mixtures in EDD, but the relative abundances, although reproducible, are low compared with those in a CID spectrum acquired on an ion trap. The application of principal component analysis (PCA) presents a multivariate approach to determining the uronic acid stereochemistry spectra of these GAGs by taking advantage of the reproducible peak distributions produced by electron detachment.

  11. Production of furans from pulp sheet over sulfated solid acid catalysts

    Directory of Open Access Journals (Sweden)

    Hongdan Zhang

    2012-11-01

    Full Text Available Furans are high value-added biomass-derived chemicals that can be used to replace petrochemicals. In this study, sulfated solid acid catalysts were prepared by precipitation and impregnation and were used for the conversion of a cellulosic pulp sheet into furans. The physicochemical properties of the prepared sulfated solid acid with different calcination temperatures and different mol ratios of Ti-Al were characterized using XRD, elemental analysis, TG, and NH3-TPD. Furthermore, the effects of various processing parameters such as temperature, time, and catalyst dosage on the reaction performance were studied. The combined yield of 5-hydroxymethyl-furfural and furfural reached 8.9% and 4.5% of pulp sheet mass with a 5% dosage of SO42-/TiO2-Al2O3 catalyst at 220 oC for 30 min. The activity for recovered catalyst was also investigated in this study.

  12. A quantitative test of infrared optical constants for supercooled sulphuric and nitric acid droplet aerosols

    Directory of Open Access Journals (Sweden)

    R. Wagner

    2003-05-01

    Full Text Available In situ Fourier transform infrared (FTIR extinction spectra of supercooled H2SO4/H2O and HNO3/H2O solution droplets were recorded in the large coolable aerosol chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere of Forschungszentrum Karlsruhe for a range of aerosol compositions and at temperatures extending down to 192 K. The measured spectra were quantitatively analysed in terms of aerosol composition and mass concentration by using Mie theory in combination with published refractive index data as input parameters. Simultaneously, total sulphuric acid and nitric acid mass concentrations from filter analysis and total water concentrations measured with the Lyman-a hygrometer of Forschungszentrum Jülich were used to calculate the aerosol composition at thermodynamic equilibrium inside the aerosol chamber. By comparing these measured aerosol parameters with those retrieved from the analysis of the FTIR spectra, the accuracy of the literature data sets of refractive indices could be assessed. In summary, four data sets were tested in the H2SO4/H2O system as well as two data sets in the HNO3/H2O system, partly revealing significant discrepancies in the retrieved aerosol properties. Potential explanations for these differences are discussed in this paper.

  13. Stratospheric aerosol acidity, density, and refractive index deduced from SAGE 2 and NMC temperature data

    Science.gov (United States)

    Yue, G. K.; Poole, L. R.; Wang, P.-H.; Chiou, E. W.

    1994-01-01

    Water vapor concentrations obtained by the Stratospheric Aerosol and Gas Experiment 2 (SAGE 2) and collocated temperatures provided by the National Meteorological Center (NMC) from 1986 to 1990 are used to deduce seasonally and zonally averaged acidity, density, and refractive index of stratospheric aerosols. It is found that the weight percentage of sulfuric acid in the aerosols increases from about 60 just above the tropopause to about 86 at 35 km. The density increases from about 1.55 to 1.85 g/cu cm between the same altitude limits. Some seasonal variations of composition and density are evident at high latitudes. The refractive indices at 1.02, 0.694, and 0.532 micrometers increase, respectively, from about 1.425, 1.430, and 1.435 just above the tropopause to about 1.445, 1.455, and 1.458 at altitudes above 27 km, depending on the season and latitude. The aerosol properties presented can be used in models to study the effectiveness of heterogeneous chemistry, the mass loading of stratospheric aerosols, and the extinction and backscatter of aerosols at different wavelengths. Computed aerosol surface areas, rate coefficients for the heterogeneous reaction ClONO2 + H2O yields HOCl + HNO3 and aerosol mass concentrations before and after the Pinatubo eruption in June 1991 are shown as sample applications.

  14. Soil Quality Assessment of Acid Sulfate Paddy Soils with Different Productivities in Guangdong Province, China

    Institute of Scientific and Technical Information of China (English)

    LIU Zhan-jun; ZHOU Wei; SHEN Jian-bo; LI Shu-tian; LIANG Guo-qing; WANG Xiu-bin; SUN Jing-wen; AI Chao

    2014-01-01

    Land conversion is considered an effective measure to ensure national food security in China, but little information is available on the quality of low productivity soils, in particular those in acid sulfate soil regions. In our study, acid sulfate paddy soils were divided into soils with high, medium and low levels based on local rice productivity, and 60 soil samples were collected for analysis. Twenty soil variables including physical, chemical and biochemical properties were determined. Those variables that were signiifcantly different between the high, medium and low productivity soils were selected for principal component analysis, and microbial biomass carbon (MBC), total nitrogen (TN), available silicon (ASi), pH and available zinc (AZn) were retained in the minimum data set (MDS). After scoring the MDS variables, they were integrated to calculate a soil quality index (SQI), and the high, medium and low productivity paddy soils received mean SQI scores of 0.95, 0.83 and 0.60, respectively. Low productivity paddy soils showed worse soil quality, and a large discrepancy was observed between the low and high productivity paddy soils. Lower MBC, TN, ASi, pH and available K (AK) were considered as the primary limiting factors. Additionally, all the soil samples collected were rich in available P and AZn, but deifcient in AK and ASi. The results suggest that soil AK and ASi deifciencies were the main limiting factors for all the studied acid sulfate paddy soil regions. The application of K and Si on a national basis and other sustainable management approaches are suggested to improve rice productivity, especially for low productivity paddy soils. Our results indicated that there is a large potential for increasing productivity and producing more cereals in acid sulfate paddy soil regions.

  15. Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A., E-mail: jimfield@email.arizona.edu

    2016-05-05

    Highlights: • Electron donor from zero-valent iron (ZVI) drives sulfate reduction to sulfide. • Sulfide converts soluble heavy metals into sulfide minerals. • Excess sulfide is sequestered by iron preventing discharge. • Corrosion of ZVI consumes acidity in acid rock drainage. • ZVI as reactive material outlasted limestone in removing heavy metals. - Abstract: This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor.

  16. Obtaining of barium sulfate from solution formed after desulfation of the active mass of scrap lead-acid batteries

    Directory of Open Access Journals (Sweden)

    O. A. Kalko

    2014-03-01

    Full Text Available Analyses of literature data about processes for solution utilization formed after desulfation of the active mass of scrap lead-acid batteries is performed. Optimal conditions for obtaining of barium sulfate sediment from ammonium sulfate solute and chemically pure Ba(OH2×8H2O и BaCl2×2H2O were found experimentally. In laboratory the commercial barium sulfate from sulfate solutions, that are waste of recycling process of battery scrap, with application of chloride and barium hydroxide was production. The possibility of using this product were discussed.

  17. Effects of salbutamol aerosol combined with magnesium sulfate on T-lymphocyte subgroup and Th1/Th2 cytokines of pediatric asthma

    Science.gov (United States)

    Diao, Min; Min, Jie; Guo, Fei; Zhang, Chong-Lin

    2017-01-01

    The aim of the study was to analyze the effects of the intravenous infusion of salbutamol aerosol combined with magnesium sulfate in the treatment of pediatric asthma and the subsequent effects on the levels of T-lymphocyte subgroups and Th1/Th2 cytokines. A total of 86 patients with pediatric asthma, first diagnosed and treated at the Xuzhou Children's Hospital, were continuously selected and randomly divided into an observation group of 44 cases and control group of 42 cases. The patients in the control group were treated with budesonide atomization inhalation, while the children in the observation group were treated with intravenous infusion of salbutamol aerosol combined with magnesium sulfate. The therapeutic effects in the groups were compared. After treatment, the levels of serum CD3+ and CD8+ decreased when compared to before treatment; the levels of CD4+ and CD4+/CD8+ also increased, but the observation group had more significant improvement. Differences were statistically significant (P<0.05). After treatment, the levels of serum interleukin-2 (IL-2) and interferon-γ (IFN-γ) increased when compared to before, while levels of IL-4 and IL-6 decreased, and the observation group had more significant improvement. The differences were statistically significant (P<0.05). After treatment, the levels of VT, t-PTEF/t-E, MTIF/MTEF and TEF75/PTEF increased when compared to before; the observation group had more significant improvement. The differences were statistically significant (P<0.05). The effective rate and degree of treatment for the observation group were significantly higher than those of the control group and differences were statistically significant (P<0.05). The intravenous infusion of salbutamol aerosol combined with magnesium sulfate in the treatment of pediatric asthma can significantly improve therapeutic effects and lung functions, improve immune functions and relieve inflammatory reactions. Therefore, it indicates better clinical application and

  18. Size Distributions of Aerosol Sulfates and Nitrates in Beijing during the 2008 Olympic Games: Impacts of Pollution Control Measures and Regional Transport

    Institute of Scientific and Technical Information of China (English)

    WANG Xinfeng; WANG Tao; Ravi Kant PATHAK; Mattias HALLQUIST; GAO Xiaomei; NIE Wei; XUE Likun

    2013-01-01

    For the 2008 Olympic Games,drastic control measures were implemented on industrial and urban emissions of sulfur dioxide (SO2),nitrogen oxides (NOx) and other pollutants to address the issues of poor air quality in Beijing.To investigate the effects of SO2 and NOx reductions on the particulate sulfate and nitrate concentrations as well as their size distributions,size-segregated aerosol samples were collected using micro-orifice uniform deposit impactors (MOUDIs) at urban and downwind rural sites in Beijing before and after full-scale controls.During the sampling period,the mass concentrations of fine particles (PM1.8) at the urban and rural sites were 94.0 and 85.9 μg m-3,respectively.More than 90% of the sulfates and ~60%of nitrates formed as fine particles.Benefiting from the advantageous meteorological conditions and the source controls,sulfates were observed in rather low concentrations and primarily in condensation mode during the Olympics.The effects of the control measures were separately analyzed for the northerly and the southerly air-mass-dominated days to account for any bias.After the control measures were implemented,PM,sulfates,and nitrates were significantly reduced when the northerly air masses prevailed,with a higher percentage of reduction in larger particles.The droplet mode particles,which dominated the sulfates and nitrates before the controls were implemented,were remarkably reduced in mass concentration after the control measures were implemented.Nevertheless,when the polluted southerly air masses prevailed,the local source control measures in Beijing did not effectively reduce the ambient sulfate concentration due to the enormous regional contribution from the North China Plain.

  19. Size distributions of aerosol sulfates and nitrates in Beijing during the 2008 Olympic Games: Impacts of pollution control measures and regional transport

    Science.gov (United States)

    Wang, Xinfeng; Wang, Tao; Pathak, Ravi Kant; Hallquist, Mattias; Gao, Xiaomei; Nie, Wei; Xue, Likun; Gao, Jian; Gao, Rui; Zhang, Qingzhu; Wang, Wenxing; Wang, Shulan; Chai, Fahe; Chen, Yizhen

    2013-03-01

    For the 2008 Olympic Games, drastic control measures were implemented on industrial and urban emissions of sulfur dioxide (SO2), nitrogen oxides (NO x ) and other pollutants to address the issues of poor air quality in Beijing. To investigate the effects of SO2 and NO x reductions on the particulate sulfate and nitrate concentrations as well as their size distributions, size-segregated aerosol samples were collected using micro-orifice uniform deposit impactors (MOUDIs) at urban and downwind rural sites in Beijing before and after full-scale controls. During the sampling period, the mass concentrations of fine particles (PM1.8) at the urban and rural sites were 94.0 and 85.9 μg m-3, respectively. More than 90% of the sulfates and ˜60% of nitrates formed as fine particles. Benefiting from the advantageous meteorological conditions and the source controls, sulfates were observed in rather low concentrations and primarily in condensation mode during the Olympics. The effects of the control measures were separately analyzed for the northerly and the southerly air-mass-dominated days to account for any bias. After the control measures were implemented, PM, sulfates, and nitrates were significantly reduced when the northerly air masses prevailed, with a higher percentage of reduction in larger particles. The droplet mode particles, which dominated the sulfates and nitrates before the controls were implemented, were remarkably reduced in mass concentration after the control measures were implemented. Nevertheless, when the polluted southerly air masses prevailed, the local source control measures in Beijing did not effectively reduce the ambient sulfate concentration due to the enormous regional contribution from the North China Plain.

  20. Sulfate reduction at low pH to remediate acid mine drainage

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez-Andrea, Irene, E-mail: irene.sanchezandrea@wur.nl [Departamento de Biología Molecular, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Laboratory of Microbiology, Wageningen University, Dreijenplein 10, 6703 HB Wageningen (Netherlands); Sanz, Jose Luis [Departamento de Biología Molecular, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Bijmans, Martijn F.M. [Wetsus, Centre of Sustainable Water Technology, P.O. Box 1113, 8900 CC Leeuwarden (Netherlands); Stams, Alfons J.M. [Laboratory of Microbiology, Wageningen University, Dreijenplein 10, 6703 HB Wageningen (Netherlands); IBB – Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, 4710-057 Braga (Portugal)

    2014-03-01

    Highlights: • Acid mine drainage (AMD) is an important environmental concern. • Remediation through biological sulfate reduction and metal recovery can be applied for AMD. • Microbial community composition has a major impact on the performance of bioreactors to treat AMD. • Acidophilic SRB are strongly influenced by proton, sulfide and organic acids concentration. - Abstract: Industrial activities and the natural oxidation of metallic sulfide-ores produce sulfate-rich waters with low pH and high heavy metals content, generally termed acid mine drainage (AMD). This is of great environmental concern as some heavy metals are highly toxic. Within a number of possibilities, biological treatment applying sulfate-reducing bacteria (SRB) is an attractive option to treat AMD and to recover metals. The process produces alkalinity, neutralizing the AMD simultaneously. The sulfide that is produced reacts with the metal in solution and precipitates them as metal sulfides. Here, important factors for biotechnological application of SRB such as the inocula, the pH of the process, the substrates and the reactor design are discussed. Microbial communities of sulfidogenic reactors treating AMD which comprise fermentative-, acetogenic- and SRB as well as methanogenic archaea are reviewed.

  1. Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia.

    Science.gov (United States)

    Kinsela, Andrew S; Collins, Richard N; Waite, T David

    2011-02-01

    Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.

  2. Uptake and diffusion of short chain alcohols into sulfuric acid and ammonium bisulfate solutions: considering the role of water in secondary organic aerosol formation.

    Science.gov (United States)

    van Loon, L. L.; Minor, R. N.; Allen, H. C.

    2006-12-01

    Secondary organic aerosol formation is of great interest since it may constitute an important fraction of tropospheric aerosols. These aerosols often contain a significant amount of sulfuric acid (40-80 wt%), which can be partially neutralized by ammonia, the most abundant basic species in the atmosphere. We have investigated the uptake of short-chain alcohols (n=1, 4, 6) by sulfuric acid and ammonium bisulfate solutions. First, methanol-sulfuric acid solutions were investigated using Raman spectroscopy. In 70+ wt% solutions of sulfuric acid, the formation of methyl sulfate was observed. In solutions of 70 wt% sulfuric acid or less no reaction was observed. While sulfuric acid is partially neutralized by ammonia, ammonium bisulfate is still quite acidic (pH 2). Studies have shown enhanced oxidation of gas-phase species in the presence of acidic particles such as NH4HSO4,1 suggesting a reaction between the particles and organic species. Solutions of ammonium bisulfate and methanol were investigated, but no methyl sulfate was detected. The surface enhancement of alcohols on sulfuric acid solutions was also investigated using sum frequency generation spectroscopy. From all these experiments we conclude that the formation of organosulfates, and therefore possible aerosol growth, is controlled by the amount of water present in the system. Second, Raman spectroscopy was used to determine the diffusion coefficients of methanol in sulfuric acid solutions. This method allows the diffusion of gas-phase methanol into aqueous solutions to be monitored simply using a Raman probe over the course of several hours. From the time data we are able to extract the diffusion coefficients. We have determined DAB = (1.7 ± 0.2) x 10^{-5} cm2/s for methanol into water and DAB = (2.5 ± 0.5) x 10^{-5} cm2/s for methanol into 96.6 wt% sulfuric acid at 293 K. 1. M. Jang, N. M. Czoschke, A. L. Northcross, Environ. Sci. Technol., 39, 164 (2005).

  3. Sulfated Steroid–Amino Acid Conjugates from the Irish Marine Sponge Polymastia boletiformis

    Directory of Open Access Journals (Sweden)

    Vangelis Smyrniotopoulos

    2015-03-01

    Full Text Available Antifungal bioactivity-guided fractionation of the organic extract of the sponge Polymastia boletiformis, collected from the west coast of Ireland, led to the isolation of two new sulfated steroid-amino acid conjugates (1 and 2. Extensive 1D and 2D NMR analyses in combination with quantum mechanical calculations of the electronic circular dichroism (ECD spectra, optical rotation, and 13C chemical shifts were used to establish the chemical structures of 1 and 2. Both compounds exhibited moderate antifungal activity against Cladosporium cucumerinum, while compound 2 was also active against Candida albicans. Marine natural products containing steroidal and amino acid constituents are extremely rare in nature.

  4. Detailed predictive mapping of acid sulfate soil occurrence using electromagnetic induction data

    DEFF Research Database (Denmark)

    Beucher, Amélie; Boman, A; Mattbäck, S

    Acid sulfate soils are often called the nastiest soils in the world (Dent & Pons, 1995). Releasing a toxic combination of acidity and metals into the recipient watercourses and estuaries, these soils represent a crucial environmental problem. Moreover, these soils can have a considerable economic...... occurrence. Different machine learning approaches will be assessed over a field located in western Finland, using soil observations and various environmental predictors (Quaternary geology maps, EM data collected from a DUALEM proximal sensor, and remote sensing data, such as airborne gamma-radiometric data...

  5. The NH4+-NO3--Cl--SO42--H2O aerosol system and its gas phase precursors at a pasture site in the Amazon Basin: How relevant are mineral cations and soluble organic acids?

    Science.gov (United States)

    Trebs, Ivonne; Metzger, Swen; Meixner, Franz X.; Helas, Günter; Hoffer, AndráS.; Rudich, Yinon; Falkovich, Alla H.; Moura, Marcos A. L.; da Silva, Rosiberto S.; Artaxo, Paulo; Slanina, Jacob; Andreae, Meinrat O.

    2005-04-01

    Real-time measurements of ammonia, nitric acid, hydrochloric acid, sulfur dioxide and the water-soluble inorganic aerosol species, ammonium, nitrate, chloride, and sulfate were performed at a pasture site in the Amazon Basin (Rondônia, Brazil). The measurements were made during the late dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions) using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC). Measurements were conducted from 12 September to 14 November 2002 within the framework of LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate). Real-time data were combined with measurements of sodium, potassium, calcium, magnesium, and low-molecular weight (LMW) polar organic acids determined on 12-, 24-, and 48-hours integrated filter samples. The contribution of inorganic species to the fine particulate mass (Dp ≤ 2.5 μm) was frequently below 20% by mass, indicating the preponderance of organic matter. The measured concentration products of NH3 × HNO3 and NH3 × HCl persistently remained below the theoretical equilibrium dissociation constants of the NH3/HNO3/NH4NO3 and NH3/HCl/NH4Cl systems during daytime (RH 90%) fine-mode NH4NO3 and NH4Cl are predicted to be formed in the aqueous aerosol phase. Probably, Cl- was driven out of the aerosol phase largely by reaction of pyrogenic KCl with HNO3 and H2SO4. As shown by an updated version of the equilibrium simplified aerosol model (EQSAM2), which incorporates mineral aerosol species and lumped LMW polar organic acids, daytime aerosol NH4+ was mainly balanced by organic compounds.

  6. Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

    Science.gov (United States)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

    2011-09-01

    The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

  7. Preparation of metal-resistant immobilized sulfate reducing bacteria beads for acid mine drainage treatment.

    Science.gov (United States)

    Zhang, Mingliang; Wang, Haixia; Han, Xuemei

    2016-07-01

    Novel immobilized sulfate-reducing bacteria (SRB) beads were prepared for the treatment of synthetic acid mine drainage (AMD) containing high concentrations of Fe, Cu, Cd and Zn using up-flow anaerobic packed-bed bioreactor. The tolerance of immobilized SRB beads to heavy metals was significantly enhanced compared with that of suspended SRB. High removal efficiencies of sulfate (61-88%) and heavy metals (>99.9%) as well as slightly alkaline effluent pH (7.3-7.8) were achieved when the bioreactor was fed with acidic influent (pH 2.7) containing high concentrations of multiple metals (Fe 469 mg/L, Cu 88 mg/L, Cd 92 mg/L and Zn 128 mg/L), which showed that the bioreactor filled with immobilized SRB beads had tolerance to AMD containing high concentrations of heavy metals. Partially decomposed maize straw was a carbon source and stabilizing agent in the initial phase of bioreactor operation but later had to be supplemented by a soluble carbon source such as sodium lactate. The microbial community in the bioreactor was characterized by denaturing gradient gel electrophoresis (DGGE) and sequencing of partial 16S rDNA genes. Synergistic interaction between SRB (Desulfovibrio desulfuricans) and co-existing fermentative bacteria could be the key factor for the utilization of complex organic substrate (maize straw) as carbon and nutrients source for sulfate reduction.

  8. Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron.

    Science.gov (United States)

    Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A

    2016-05-05

    This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor.

  9. Mechanistic modeling of biocorrosion caused by biofilms of sulfate reducing bacteria and acid producing bacteria.

    Science.gov (United States)

    Xu, Dake; Li, Yingchao; Gu, Tingyue

    2016-08-01

    Biocorrosion is also known as microbiologically influenced corrosion (MIC). Most anaerobic MIC cases can be classified into two major types. Type I MIC involves non-oxygen oxidants such as sulfate and nitrate that require biocatalysis for their reduction in the cytoplasm of microbes such as sulfate reducing bacteria (SRB) and nitrate reducing bacteria (NRB). This means that the extracellular electrons from the oxidation of metal such as iron must be transported across cell walls into the cytoplasm. Type II MIC involves oxidants such as protons that are secreted by microbes such as acid producing bacteria (APB). The biofilms in this case supply the locally high concentrations of oxidants that are corrosive without biocatalysis. This work describes a mechanistic model that is based on the biocatalytic cathodic sulfate reduction (BCSR) theory. The model utilizes charge transfer and mass transfer concepts to describe the SRB biocorrosion process. The model also includes a mechanism to describe APB attack based on the local acidic pH at a pit bottom. A pitting prediction software package has been created based on the mechanisms. It predicts long-term pitting rates and worst-case scenarios after calibration using SRB short-term pit depth data. Various parameters can be investigated through computer simulation.

  10. Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols.

    Science.gov (United States)

    Jang, Myoseon; Carroll, Brian; Chandramouli, Bharadwaj; Kamens, Richard M

    2003-09-01

    Aerosol growth by the heterogeneous reactions of different aliphatic and alpha,beta-unsaturated carbonyls in the presence/absence of acidified seed aerosols was studied in a 2 m long flow reactor (2.5 cm i.d.) and a 0.5-m3 Teflon film bag under darkness. For the flow reactor experiments, 2,4-hexadienal, 5-methyl-3-hexen-2-one, 2-cyclohexenone, 3-methyl-2-cyclopentenone, 3-methyl-2-cyclohexenone, and octanal were studied. The carbonyls were selected based on their reactivity for acid-catalyzed reactions, their proton affinity, and their similarity to the ring-opening products from the atmospheric oxidation of aromatics. To facilitate acid-catalyzed heterogeneous hemiacetal/acetal formation, glycerol was injected along with inorganic seed aerosols into the flow reactor system. Carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. Aldehydes were more reactive than ketones for acid-catalyzed reactions. The conjugated functionality also resulted in higher organic aerosol yieldsthan saturated aliphatic carbonyls because conjugation with the olefinic bond increases the basicity of the carbonyl leading to increased stability of the protonated carbonyl. Aerosol population was measured from a series of sampling ports along the length of the flow reactor using a scanning mobility particle sizer. Fourier transform infrared spectrometry of either an impacted liquid aerosol layer or direct reaction of carbonyls as a thin liquid layer on a zinc selenide FTIR disk was employed to demonstrate the direct transformation of chemical functional groups via the acid-catalyzed reactions. These results strongly indicate that atmospheric multifunctional organic carbonyls, which are created by atmospheric photooxidation reactions, can contribute significantly to secondary organic aerosol formation through acid-catalyzed heterogeneous reactions. Exploratory studies in 25- and 190-m3 outdoor chambers

  11. Rare Isotope Insights into Supereruptions: Rare Sulfur and Triple Oxygen Isotope Geochemistry of Stratospheric Sulfate Aerosols Absorbed on Volcanic Ash Particles

    Science.gov (United States)

    Bindeman, I. N.; Eiler, J.; Wing, B.; Farquhar, J.

    2006-12-01

    We present analyses of stable isotopic ratios of 17O/16O, 18O/16O, 34S/32S, and 33S/32S, 36S/32S of sulfate leached from volcanic ash of a series of well-known volcanic eruptions. This list covers much of the diversity of sizes and the character of volcanic eruptions. Particular emphasis is paid to the Lava Creek Tuff of Yellowstone and we present wide geographic sample coverage for this unit. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29, 30 and 3.3 permil respectively) with oxygen isotopes recording mass-independent fractionation and sulfur isotopes exhibiting mass-dependent behavior. These ranges are defined by the isotopic compositions of products of large caldera forming eruptions. Proximal ignimbrites and coarse ash typically do not contain sulfate. The presence of sulfate with Δ17O > 0.2 permil is characteristic of small distal ash particles, suggesting that sulfate aerosols were scavenged after they underwent atmospheric photochemical reactions. Additionally, sediments that embed ash layers either do not contain sulfate or contain minor sulfate with Δ17O near 0 permil, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent sulfur isotopic compositions suggest that sulfate-forming reactions did not involve photolysis of SO2, unlike the situation inferred for some pre-2.3 Ga sulfates or hypothesized to occur during the formation of sulfate associated with plinian eruptions that pierce the ozone layer. However, sulfate in the products of caldera-forming eruptions display a large δ34S range and fractionation relationships that do not follow equilibrium slopes of 0.515 and 1.90 for 33S/32S vs. 34S/32S and 36S/32S vs. 34S/32S, respectively. This implies that the sulfur isotopic characteristics of these sulfates were not set by a single stage, high-temperature equilibrium process in the volcanic plum. The data presented here are consistent with a single stage kinetic fractionation of sulfur

  12. Optical properties in the UV and visible spectral region of organic acids relevant to tropospheric aerosols

    Directory of Open Access Journals (Sweden)

    C. E. Lund Myhre

    2004-06-01

    Full Text Available Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.

  13. Optical properties in the UV and visible spectral region of organic acids relevant to tropospheric aerosols

    Directory of Open Access Journals (Sweden)

    C. E. Lund Myhre

    2004-01-01

    Full Text Available Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.

  14. On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

    OpenAIRE

    S. Schobesberger; Franchin, A.; Bianchi, F.(University of Turin, Turin, I-10125, Italy); L. Rondo; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; R. Schnitzhofer; Almeida, J; Amorim, A.; Dommen, J.; Dunne, E.M.; Ehn, M.; S. Gagné

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in th...

  15. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    OpenAIRE

    S. Schobesberger; Franchin, A.; Bianchi, F.(University of Turin, Turin, I-10125, Italy); L. Rondo; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; R. Schnitzhofer; Almeida, J; Amorim, A.; Dommen, J.; Dunne, E.M.; Ehn, M.; S. Gagné

    2014-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments wer...

  16. Photochemical organonitrate formation in wet aerosols

    Science.gov (United States)

    Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

    2016-10-01

    Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

  17. Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

    Directory of Open Access Journals (Sweden)

    Alpers Charles N

    2007-10-01

    Full Text Available Abstract Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5. The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1 preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2 stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3 reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA and denaturing gradient gel electrophoresis (DGGE analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures.

  18. Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

    Science.gov (United States)

    Church, C.D.; Wilkin, R.T.; Alpers, C.N.; Rye, R.O.; Blaine, R.B.

    2007-01-01

    Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

  19. Effect of A Long Chain Carboxylate Acid on Sodium Dodecyl Sulfate Micelle Structure: A SANS Study

    Science.gov (United States)

    Patriati, Arum; Giri Rachman Putra, Edy; Seok Seong, Baek

    2010-01-01

    The effect of a different hydrocarbon chain length of carboxylate acid, i.e. dodecanoic acid, CH3(CH)10COOH or lauric acid and hexadecanoic acid, CH3(CH2)14COOH or palmitic acid as a co-surfactant in the 0.3 M sodium dedecyl sulfate, SDS micellar solution has been studied using small angle neutron scattering (SANS). The present of lauric acid has induced the SDS structural micelles. The ellipsoid micelles structures changed significantly in length (major axis) from 22.6 Å to 37.1 Å at a fixed minor axis of 16.7 Å in the present of 0.005 M to 0.1 M lauric acid. Nevertheless, this effect did not occur in the present of palmitic acid with the same concentration range. The present of palmitic acid molecules performed insignificant effect on the SDS micelles growth where the major axis of the micelle was elongated from 22.9 Å to 25.3 Å only. It showed that the appropriate hydrocarbon chain length between surfactant and co-surfactant molecules emerged as one of the determining factors in forming a mixed micelles structure.

  20. Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions

    Science.gov (United States)

    Al-Kindi, Suad S.; Pope, Francis D.; Beddows, David C.; Bloss, William J.; Harrison, Roy M.

    2016-12-01

    A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 %. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azelaic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under both relative humidity conditions, the percentage residual of oleic acid increases with increasing particle size and the main lower molecular weight products are nonanal and oxononanoic acid. Under dry conditions, the percentage of higher molecular weight products increases with increasing particle size due to the poorer internal mixing of the larger particles. Under humidified conditions, the percentage of unreacted oleic acid is greater, except in the smallest particle fraction, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the

  1. Present and potential future contributions of sulfate, black and organic carbon aerosols from China to global air quality, premature mortality and radiative forcing

    Science.gov (United States)

    Saikawa, Eri; Naik, Vaishali; Horowitz, Larry W.; Liu, Junfeng; Mauzerall, Denise L.

    Aerosols are harmful to human health and have both direct and indirect effects on climate. China is a major contributor to global emissions of sulfur dioxide (SO 2), a sulfate (SO 42-) precursor, organic carbon (OC), and black carbon (BC) aerosols. Although increasingly examined, the effect of present and potential future levels of these emissions on global premature mortality and climate change has not been well quantified. Through both direct radiative effects and indirect effects on clouds, SO 42- and OC exert negative radiative forcing (cooling) while BC exerts positive forcing (warming). We analyze the effect of China's emissions of SO 2, SO 42-, OC and BC in 2000 and for three emission scenarios in 2030 on global surface aerosol concentrations, premature mortality, and radiative forcing (RF). Using global models of chemical transport (MOZART-2) and radiative transfer (GFDL RTM), and combining simulation results with gridded population data, mortality rates, and concentration-response relationships from the epidemiological literature, we estimate the contribution of Chinese aerosols to global annual premature mortality and to RF in 2000 and 2030. In 2000, we estimate these aerosols cause approximately 470 000 premature deaths in China and an additional 30 000 deaths globally. In 2030, aggressive emission controls lead to a 50% reduction in premature deaths from the 2000 level to 240 000 in China and 10 000 elsewhere, while under a high emissions scenario premature deaths increase 50% from the 2000 level to 720 000 in China and to 40 000 elsewhere. Because the negative RF from SO 42- and OC is larger than the positive forcing from BC, Chinese aerosols lead to global net direct RF of -74 mW m -2 in 2000 and between -15 and -97 mW m -2 in 2030 depending on the emissions scenario. Our analysis indicates that increased effort to reduce greenhouse gases is essential to address climate change as China's anticipated reduction of aerosols will result in the

  2. Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

    Science.gov (United States)

    Wang, G.; Xie, M.; Hu, S.; Gao, S.; Tachibana, E.; Kawamura, K.

    2010-07-01

    Dicarboxylic acids (C2-C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas were 1546±203 and 1728±495 ng m-3 during winter and 1236±335 and 1028±193 ng m-3 during spring. EC in the urban and the suburban atmospheres were 17±3.8 and 8.0±2.1 μg m-3 during winter and 20±5.9 and 7.1±2.7 μg m-3 during spring, while OC at the urban and suburban sites were 74±14 and 51±7.9 μg m-3 in winter and 51±20 and 23±6.1 μg m-3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring were 34±10 and 61±27 μg m-3 in the urban air and 18±7 and 32±23 μg m-3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value of sample extracts on water-soluble inorganic carbon, suggesting fugitive dust as an important source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter, indicating an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (δ13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (δ15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3-/PM10, which is possibly caused by an enhanced adsorption and

  3. Impeded Acidification of Acid Sulfate Soils in an Inten- sively Drained Sugarcane Land

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Recent research results suggest that acidification of acid sulfate soils may be inhibited in well-drained estuarine floodplains in eastern Australia by the absence of natural creek levees. The lack of natural levees has allowed the inundation of the land by regular tidal flooding prior to the construction of flood mitigation work. Such physiographical conditions prevent the development of pre-drainage pyrite-derived soil acidifica- tion that possibly occurred at many levee-protected sites in eastern Australian estuarine floodplains during extremely dry spells. Pre-drainage acidification is considered as an important condition for accumulation of soluble Fe and consequently, the creation of favourable environments for catalysed pyrite oxidation. Under current intensively drained conditions, the acid materials produced by ongoing pyrite oxidation can be rapidly removed from soil pore water by lateral leaching and acid buffering, resulting in low concentrations of soluble Fe in the pyritic layer, which could reduce the rate of pyrite oxidation.

  4. Monitoring and assessment of surface water acidification following rewetting of oxidised acid sulfate soils.

    Science.gov (United States)

    Mosley, Luke M; Zammit, Benjamin; Jolley, Ann-Marie; Barnett, Liz; Fitzpatrick, Rob

    2014-01-01

    Large-scale exposure of acid sulfate soils during a hydrological drought in the Lower Lakes of South Australia resulted in acidification of surface water in several locations. Our aim was to describe the techniques used to monitor, assess and manage these acidification events using a field and laboratory dataset (n = 1,208) of acidic to circum-neutral pH water samples. The median pH of the acidified (pH  H(+) ≈ Mn(II) > Fe(II/III)) but was about 20 % higher on average. Geochemical speciation calculations and XRD measurements indicated that solid phase minerals (schwertmannite and jarosite for Fe and jurbanite for Al) were likely controlling dissolved metal concentrations and influencing measured acidity between pH 2 and 5.

  5. Groundwater or floodwater? Assessing the pathways of metal exports from a coastal acid sulfate soil catchment.

    Science.gov (United States)

    Santos, Isaac R; de Weys, Jason; Eyre, Bradley D

    2011-11-15

    Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L(-1), respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries.

  6. The electrochemical corrosion of bulk nanocrystalline ingot iron in acidic sulfate solution.

    Science.gov (United States)

    Wang, S G; Shen, C B; Long, K; Zhang, T; Wang, F H; Zhang, Z D

    2006-01-12

    The corrosion properties of bulk nanocrystalline ingot iron (BNII) fabricated from conventional polycrystalline ingot iron (CPII) by severe rolling were investigated by means of immersion test, potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS) tests, and scanning electron microscopy (SEM) observation. These experimental results indicate that BNII possesses excellent corrosion resistance in comparison with CPII in acidic sulfate solution at room temperature. It may mainly result from different surface microstructures between CPII and BNII. However, the corrosion resistance of nanocrystalline materials is usually degraded because of their metastable microstructure nature, and the residual stress in nanocrystalline materials also can result in degradation of corrosion resistance according to the traditional point of view.

  7. Supplementing predictive mapping of acid sulfate soil occurrence with Vis-NIR spectroscopy

    DEFF Research Database (Denmark)

    Beucher, Amélie; Peng, Yi; Knadel, Maria

    . Recently, a digital soil mapping approach was assessed to create a predictive map for potential acid sulfate soil occurrence in the wetlands of Jutland (c. 6500 km2; Beucher et al., 2016). An Artificial Neural Networks method was applied using 8000 soil observations and 16 environmental variables...... occurrence in the Skjern River catchment (c. 2500 km2). Different machine learning approaches will be assessed using soil and environmental data, together with laboratory Vis-NIR spectral data available for the study area. Absorbance values (400–2500 nm) were measured for 600 soil samples with a DS2500...

  8. Application of the VH-TDMA technique to coastal ambient aerosols

    Science.gov (United States)

    Johnson, G.; Ristovski, Z.; Morawska, L.

    2004-08-01

    A newly developed VH-TDMA has been used for the first time to measure the volatile fractions and post volatilization hygroscopic growth factors of ambient aerosols in the coastal marine and urban environments. The results are compared with comparable data for laboratory generated aerosols of known composition. Measurements conducted on coastal Aitken mode particles showed volatilization behavior similar to laboratory generated aerosols composed of methane sulfonic acid and ammonium sulfate. Measurements conducted on 60 nm particles during nucleation events contained a greater fraction of material with similar volatility to ammonium sulfate than was found at other times. These particles were hygroscopic but less so than pure ammonium sulfate. Measurements conducted in the Brisbane central business district during sea breeze conditions show similar behavior to the coastal aerosol, but with additional low volatility species. This aerosol may originate from urban sources or from marine particles acquiring additional secondary aerosol species during transport.

  9. Spatial and seasonal variability of PM2.5 acidity at two Chinese megacities: insights into the formation of secondary inorganic aerosols

    Directory of Open Access Journals (Sweden)

    Z. Shi

    2012-02-01

    Full Text Available Aerosol acidity is one of the most important parameters influencing atmospheric chemistry and physics. Based on continuous field observations from January 2005 to May 2006 and thermodynamic modeling, we investigated the spatial and seasonal variations in PM2.5 acidity in two megacities in China, Beijing and Chongqing. Spatially, PM2.5 was generally more acidic in Chongqing than in Beijing, but a reverse spatial pattern was found within the two cities, with more acidic PM2.5 at the urban site in Beijing whereas the rural site in Chongqing. Ionic compositions of PM2.5 revealed that it was the higher concentrations of NO3− at the urban site in Beijing and the lower concentrations of Ca2+ within the rural site in Chongqing that made their PM2.5 more acidic. Temporally, PM2.5 was more acidic in summer and fall than in winter, while in the spring of 2006, the acidity of PM2.5 was higher in Beijing but lower in Chongqing than that in 2005. These were attributed to the more efficient formation of nitrate relative to sulfate as a result of the influence of Asian desert dust in 2006 in Beijing and the greater wet deposition of ammonium compared to sulfate and nitrate in 2005 in Chongqing. Furthermore, simultaneous increase of PM2.5 acidity was observed from spring to early summer of 2005 in both cities. This synoptic-scale evolution of PM2.5 acidity was accompanied by the changes in air masses origins, which were influenced by the movements of a subtropical high over the northwestern Pacific in early summer. Finally, the correlations between [NO3−]/[SO42−] and [NH4+]/[SO42−] suggests that under conditions of high aerosol acidity, heterogeneous reactions became one of the major pathways for the formation of nitrate at both cities. These findings provided new insights in our understanding of the spatial and temporal variations in aerosol acidity in Beijing and Chongqing, as well as those reported in other cities in China.

  10. Effects of inhaled acid aerosols on lung mechanics: an analysis of human exposure studies.

    OpenAIRE

    Utell, M J

    1985-01-01

    There exist significant gaps in our understanding of human health effects from inhalation of pollutants associated with acid precipitation. Controlled clinical studies examine effects of criteria pollutants almost exclusively by assessing changes in lung mechanics. One constituent of acid precipitation, sulfuric acid aerosols, has been shown to induce bronchoconstriction in exercising extrinsic asthmatics at near ambient levels. These asthmatics may be an order of magnitude more sensitive to ...

  11. Sulfate-nitrate-ammonium aerosols over China: response to 2000–2015 emission changes of sulfur dioxide, nitrogen oxides, and ammonia

    Directory of Open Access Journals (Sweden)

    Y. Wang

    2013-03-01

    Full Text Available We use a chemical transport model to examine the change of sulfate-nitrate-ammonium (SNA aerosols over China due to anthropogenic emission changes of their precursors (SO2, NOx and NH3 from 2000 to 2015. From 2000 to 2006, annual mean SNA concentrations increased by about 60% over China as a result of the 60% and 80% increases in SO2 and NOx emissions. During this period, sulfate is the dominant component of SNA over South China (SC and Sichuan Basin (SCB, while nitrate and sulfate contribute equally over North China (NC. Based on emission reduction targets in the 12th (2011–2015 Five-Year Plan (FYP, China's total SO2 and NOx emissions are projected to change by −16% and +16% from 2006 to 2015, respectively. The amount of NH3 emissions in 2015 is uncertain, given the lack of sufficient information on the past and present levels of NH3 emissions in China. With no change in NH3 emissions, SNA mass concentrations in 2015 will decrease over SCB and SC compared to their 2006 levels, but increase over NC where the magnitude of nitrate increase exceeds that of sulfate reduction. This suggests that the SO2 emission reduction target set by the 12th FYP, although effective in reducing SNA over SC and SCB, will not be successful over NC, for which NOx emission control needs to be strengthened. If NH3 emissions are allowed to keep their recent growth rate and increase by +16% from 2006 to 2015, the benefit of SO2 reduction will be completely offset over all of China due to the significant increase of nitrate, demonstrating the critical role of NH3 in regulating nitrate. The effective strategy to control SNA and hence PM2.5 pollution over China should thus be based on improving understanding of current NH3 emissions and putting more emphasis on controlling NH3 emissions in the future.

  12. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

    Science.gov (United States)

    Kirk, Nordstrom D.; Blaine, McCleskey R.; Ball, J.W.

    2009-01-01

    Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH ??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values 350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

  13. Ozone oxidation of oleic acid surface films decreases aerosol cloud condensation nuclei activity

    Science.gov (United States)

    Schwier, A. N.; Sareen, N.; Lathem, T. L.; Nenes, A.; McNeill, V. F.

    2011-08-01

    Heterogeneous oxidation of aerosols composed of pure oleic acid (C18H34O2, an unsaturated fatty acid commonly found in continental and marine aerosol) by gas-phase O3 is known to increase aerosol hygroscopicity and activity as cloud condensation nuclei (CCN). Whether this trend is preserved when the oleic acid is internally mixed with other electrolytes is unknown and addressed in this study. We quantify the CCN activity of sodium salt aerosols (NaCl and Na2SO4) internally mixed with sodium oleate (SO) and oleic acid (OA). We find that particles containing roughly one monolayer of SO/OA show similar CCN activity to pure salt particles, whereas a tenfold increase in organic concentration slightly depresses CCN activity. O3 oxidation of these multicomponent aerosols has little effect on the critical diameter for CCN activation for unacidified particles at all conditions studied, and the activation kinetics of the CCN are similar in each case to those of pure salts. SO-containing particles which are acidified to atmospherically relevant pH before analysis in order to form oleic acid, however, show depressed CCN activity upon oxidation. This effect is more pronounced at higher organic concentrations. The behavior after oxidation is consistent with the disappearance of the organic surface film, supported by Köhler Theory Analysis (KTA). The κ-Köhler calculations show a small decrease in hygroscopicity after oxidation. The important implication of this finding is that oxidative aging may not always enhance the hygroscopicity of internally mixed inorganic-organic aerosols.

  14. Iron Absorption from Two Milk Formulas Fortified with Iron Sulfate Stabilized with Maltodextrin and Citric Acid

    Science.gov (United States)

    Pizarro, Fernando; Olivares, Manuel; Maciero, Eugenia; Krasnoff, Gustavo; Cócaro, Nicolas; Gaitan, Diego

    2015-01-01

    Background: Fortification of milk formulas with iron is a strategy widely used, but the absorption of non-heme iron is low. The purpose of this study was to measure the bioavailability of two iron fortified milk formulas designed to cover toddlers’ nutritional needs. These milks were fortified with iron sulfate stabilized with maltodextrin and citric acid. Methods: 15 women (33–47 years old) participated in study. They received on different days, after an overnight fast, 200 mL of Formula A; 200 mL of Formula B; 30 mL of a solution of iron and ascorbic acid as reference dose and 200 mL of full fat cow’s milk fortified with iron as ferrous sulfate. Milk formulas and reference dose were labeled with radioisotopes 59Fe or 55Fe, and the absorption of iron measured by erythrocyte incorporation of radioactive Fe. Results: The geometric mean iron absorption corrected to 40% of the reference dose was 20.6% for Formula A and 20.7% for Formula B, versus 7.5% of iron fortified cow’s milk (p < 0.001). The post hoc Sheffé indeed differences between the milk formulas and the cow’s milk (p < 0.001). Conclusion: Formulas A and B contain highly bioavailable iron, which contributes to covering toddlers’ requirements of this micronutrient. PMID:26529007

  15. Iron Absorption from Two Milk Formulas Fortified with Iron Sulfate Stabilized with Maltodextrin and Citric Acid

    Directory of Open Access Journals (Sweden)

    Fernando Pizarro

    2015-10-01

    Full Text Available Background: Fortification of milk formulas with iron is a strategy widely used, but the absorption of non-heme iron is low. The purpose of this study was to measure the bioavailability of two iron fortified milk formulas designed to cover toddlers´ nutritional needs. These milks were fortified with iron sulfate stabilized with maltodextrin and citric acid. Methods: 15 women (33–47 years old participated in study. They received on different days, after an overnight fast, 200 mL of Formula A; 200 mL of Formula B; 30 mL of a solution of iron and ascorbic acid as reference dose and 200 mL of full fat cow’s milk fortified with iron as ferrous sulfate. Milk formulas and reference dose were labeled with radioisotopes 59Fe or 55Fe, and the absorption of iron measured by erythrocyte incorporation of radioactive Fe. Results: The geometric mean iron absorption corrected to 40% of the reference dose was 20.6% for Formula A and 20.7% for Formula B, versus 7.5% of iron fortified cow’s milk (p < 0.001. The post hoc Sheffé indeed differences between the milk formulas and the cow’s milk (p < 0.001. Conclusion: Formulas A and B contain highly bioavailable iron, which contributes to covering toddlers´ requirements of this micronutrient.

  16. Calcium Sulfate with Stearic Acid as an Encouraging Carrier for Reindeer Bone Protein Extract

    Directory of Open Access Journals (Sweden)

    Pekka Jalovaara

    2011-07-01

    Full Text Available Various bone proteins and growth factors in specific concentrations are required for bone formation. If the body cannot produce sufficient quantities of these factors, bone trauma can be healed with an implant that includes the required factors in a carrier. This study was designed to evaluate various calcium salt candidates that can be used as carrier with reindeer bone protein extract to induce ectopic bone formation in the muscle pouch model of mouse. The bone protein extract was either impregnated into the disc form of carrier or mixed with carrier powder before implantation. The radiographic analysis indicated increased bone formation in all of the active groups containing the bone protein extract compared to the controls within 21 days follow-up. The highest bone formation was seen in the group with calcium sulfate with stearic acid where new bone and calcified cartilage were clearly visible. The greatest bone formation occurred in the groups that had bone protein extract readily available. This indicates that the bone forming factors in sufficient concentrations are required at the early stage of bone formation. The calcium sulfate with stearic acid was the most suitable and effective carrier for reindeer bone protein extract.

  17. Seasonal variation of gypsum in aerosol and its effect on the acidity of wet precipitation on the Japan sea side of Japan

    Science.gov (United States)

    Zhou, Guoping; Tazaki, Kazue

    Variations of mineral concentrations in aerosols collected weekly for a 1 yr period (from October 1992 to September 1993) on Matsue, Shimane Prefecture, Japan, were investigated by X-ray powder diffraction (XRD) analysis. Major elemental concentrations were measured by energy dispersive X-ray analysis (EDX). Sulfate minerals in aerosol include gypsum, ferricopiapite, metavoltine and glauberite. Gypsum showed two high concentration peaks during spring and early winter, which was consistent with that of clay minerals and quartz. The ratios of gypsum to clay minerals, quartz and calcite, respectively, showed an increase of gypsum in spring. A non-agreement of concentration distribution between calcite and other soil minerals during spring implies a conversion of calcite to gypsum during transport. Individual particle analyses by EDX revealed large amounts of S-rich submicrometer particles coated on the surface of minerals. A sequence favorable to be attached by S constituents was calcite (83%) > clay minerals (68%) > fly ash (55) > quartz and feldspars (36%) The reaction between calcite and simulated acid rain solution with pHs of 3, 4 and 5 showed a formation of gypsum in 12 h, indicating that the conversion of calcite to gypsum is possible in the presence of sulfuric acid or (NH 4) 2 SO 4 aerosols during transport from the Asian continent to the Japan Islands.

  18. Sulfate- and sialic acid-containing glycolipids inhibit DNA polymerase alpha activity.

    Science.gov (United States)

    Simbulan, C M; Taki, T; Tamiya-Koizumi, K; Suzuki, M; Savoysky, E; Shoji, M; Yoshida, S

    1994-03-16

    The effects of various glycolipids on the activity of immunoaffinity-purified calf thymus DNA polymerase alpha were studied in vitro. Preincubation with sialic acid-containing glycolipids, such as sialosylparagloboside (SPG), GM3, GM1, and GD1a, and sulfatide (cerebroside sulfate ester, CSE) dose-dependently inhibited the activity of DNA polymerase alpha, while other glycolipids, as well as free sphingosine and ceramide did not. About 50% inhibition was achieved by preincubating the enzyme with 2.5 microM of CSE, 50 microM of SPG or GM3, and 80 microM of GM1. Inhibition was noncompetitive with both the DNA template and the substrate dTTP, as well as with the other dNTPs. Since the inhibition was largely reversed by the addition of 0.05% Nonidet P40, these glycolipids may interact with the hydrophobic region of the enzyme protein. Apparently, the sulfate moiety in CSE and the sialic acid moiety in gangliosides were essential for the inhibition since neither neutral glycolipids (i.e., glucosylceramide, galactosylceramide, lactosylceramide) nor asialo-gangliosides (GA1 and GA2) showed any inhibitory effect. Furthermore, the ceramide backbone was also found to be necessary for maximal inhibition since the inhibition was largely abolished by substituting the lipid backbone with cholesterol. Increasing the number of sialic acid moieties per molecule further enhanced the inhibition, while elongating the sugar chain diminished it. It was clearly shown that the N-acetyl residue of the sialic acid moiety is particularly essential for inhibition by both SPG and GM3 because the loss of this residue or substitution with a glycolyl residue completely negated their inhibitory effect on DNA polymerase alpha activity.

  19. Distribution of iron- and sulfate-reducing bacteria across a coastal acid sulfate soil (CASS environment: implications for passive bioremediation by tidal inundation

    Directory of Open Access Journals (Sweden)

    Yu-Chen eLing

    2015-07-01

    Full Text Available Coastal acid sulfate soils (CASS constitute a serious and global environmental problem. Oxidation of iron sulfide minerals exposed to air generates sulfuric acid with consequently negative impacts on coastal and estuarine ecosystems. Tidal inundation represents one current treatment strategy for CASS, with the aim of neutralizing acidity by triggering microbial iron- and sulfate-reduction and inducing the precipitation of iron-sulfides. Although well-known functional guilds of bacteria drive these processes, their distributions within CASS environments, as well as their relationships to tidal cycling and the availability of nutrients and electron acceptors, are poorly understood. These factors will determine the long-term efficacy of passive CASS remediation strategies. Here we studied microbial community structure and functional guild distribution in sediment cores obtained from ten depths ranging from 0-20 cm in three sites located in the supra-, inter- and sub-tidal segments, respectively, of a CASS-affected salt marsh (East Trinity, Cairns, Australia. Whole community 16S rRNA gene diversity within each site was assessed by 454 pyrotag sequencing and bioinformatic analyses in the context of local hydrological, geochemical and lithological factors. The results illustrate spatial overlap, or close association, of iron- and sulfate-reducing bacteria in an environment rich in organic matter and controlled by parameters such as acidity, redox potential, degree of water saturation, and mineralization. The observed spatial distribution implies the need for empirical understanding of the timing, relative to tidal cycling, of various terminal electron-accepting processes that control acid generation and biogeochemical iron and sulfur cycling.

  20. Using Australian Acidic Playa Lakes as Analogs for Phyllosilicate and Sulfate Depositional Environments on Mars

    Science.gov (United States)

    Baldridge, A. M.; Michalski, J.; Kargel, J.; Hook, S.; Marion, G.; Crowley, J.; Bridges, N.; Brown, A.; Ribeiro da Luz, B.; de Souza Filho, C. R.; Thomson, B.

    2008-12-01

    Recent work on the origin of martian sulfates and their relationship to phyllosilicate deposits suggest that these deposits formed in different eras of Mars' history, under distinct environmental conditions. In southwestern Meridiani Planum phyllosilicates exist in close proximity to sulfate deposits. One possible explanation for this relationship is that it is an unconformable stratigraphic sequence, representing a significant change in aqueous geochemical conditions over time. Specifically, it may be interpreted to record a change in environment from neutral pH aqueous alteration in the Noachian to an acidic evaporitic system in the late Noachian to the Hesperian. On Earth, two different geochemical systems need not be evoked to explain such chemical variation. Acidic playa lakes in Western Australia have large pH differences separated by only a few tens of meters and demonstrate how highly variable chemistries can coexist over short distances in natural environments. Playa lakes on Earth tend to be dominated by lateral flow of water and salts leading to lateral chemical variation. Heterogeneity of playa mineralogy in Australia is due to the varied source rocks of brines and the mixing of dilute oxidizing brines and freshwater with the saturated evaporitic brines. This is evidenced by the ferricretes in the near-shore environment and more soluble phases in basin interiors. Playa lakes on Mars would be much larger than their terrestrial counterparts, leading to the prevalence of large-scale surface and crustal advection of water and salt rather than short-distance lateral flow, except at lake boundaries. Little or no influx of freshwater would preclude the formation of playa rim (e.g., crater rim) ferricretes and silcretes. Instead, we expect to see mainly vertical facies changes, and any diachronous lateral facies changes are expected to occur on very large spatial scales. Comparison of high spatial resolution, hyperspectral airborne data for Australian playa

  1. N-alkanes, fatty acid esters, and fatty acid salts in size fractionated aerosols collected over the Mediterranean Sea

    Energy Technology Data Exchange (ETDEWEB)

    Sicre, M.A.; Marty, J.C.; Saliot, A. (Univ. Pierre et Marie Curie, Paris (France))

    1990-03-20

    The {und n}-alkanes, fatty acid esters, and fatty acid salts have been analyzed in size fractionated aerosols collected over the Mediterranean Sea using a five-stage cascade impactor. Two main sources of {und n}-alkanes have been identified: terrestrially derived {und n}-alkanes evenly distributed over the whole particle size spectrum and anthropogenic {und n}-alkanes predominantly carried by submicron particles. The comparison between the fatty acid ester (FAE) and fatty acid salt (FAS) particle size distributions allowed an important contribution to be ascertained of the marine source in aerosols ranging from 7.2 to 3.0 {mu}m under rough weather conditions that may be due to larger bubble produced particles. In contrast, FAE and FAS were evenly distributed from the first to the fifth stage, when collected during calm sea surface conditions. Higher values of the degree of unsaturation of FAE and FAS were associated with mass concentration maxima observed on stages 2 and 3 in IMP1 aerosol sample whereas lower values were found on the other stages in the same sample, and over the whole particle size spectrum in IMP2 aerosol sample collected during calm weather conditions. The data the authors present here are discussed in terms of jet and film drop ejections and degradation processes.

  2. Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

    Institute of Scientific and Technical Information of China (English)

    Qing-quan Lin; Guo-hua Gu; Hui Wang; Ren-feng Zhu; You-cai Liu; and Jian-gang Fu

    2016-01-01

    In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leach-ing efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sul-furic acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respec-tively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent ac-tivation energy of 12.28 kJ·mol−1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO4·H2O.

  3. Viscosity controls humidity dependence of N2O5 uptake to citric acid aerosol

    Directory of Open Access Journals (Sweden)

    G. Gržinić

    2015-08-01

    Full Text Available The heterogeneous loss of dinitrogen pentoxide (N2O5 to aerosol particles has a significant impact on the night time nitrogen oxide cycle and therefore the oxidative capacity in the troposphere. Using a 13N short lived radioactive tracer method we studied the uptake kinetics of N2O5 on citric acid aerosol particles as a function of relative humidity (RH. The results show that citric acid exhibits lower reactivity than similar di- and polycarboxylic acids, with uptake coefficients between ~ 3 × 10−4–~ 3 × 10−3 depending on humidity (17–70 % RH. This humidity dependence can be explained by a changing viscosity and, hence, diffusivity in the organic matrix. Since the viscosity of highly concentrated citric acid solutions is not well established, we present four different parameterizations of N2O5 diffusivity based on the available literature data or estimates for viscosity and diffusivity. Above 50 % RH, uptake is consistent with the reacto-diffusive kinetic regime whereas below 50 % RH, the uptake coefficient is higher than expected from hydrolysis of N2O5 within the bulk of the particles, and the uptake kinetics may be limited by loss on the surface only. This study demonstrates the impact of viscosity in highly oxidized and highly functionalized secondary organic aerosol material on the heterogeneous chemistry of N2O5 and may explain some of the unexpectedly low loss rates to aerosol derived from field studies.

  4. Role of basic amino acids in the interaction of bindin with sulfated fucans.

    Science.gov (United States)

    DeAngelis, P L; Glabe, C G

    1988-10-18

    Bindin, the acrosomal sperm adhesion protein of the sea urchin Strongylocentrotus purpuratus, binds specifically and with high affinity (Kd = 10(-8) M) to egg sulfated fucans in the high ionic strength milieu of seawater (0.55 M salt). Previous studies indicated that the negatively charged sulfate groups of the polysaccharide are critical for binding which suggested a binding mechanism involving basic residues of bindin. We found that the binding of fucan to bindin or polyarginine is stable at the ionic strength of seawater, whereas the binding of fucan to polylysine or polyhistidine is inhibited by 50% or more at this ionic strength. Group-specific modification of either arginine, lysine, or histidine residues of bindin results in a substantial inactivation of fucan binding activity. Preincubation of bindin with fucan can almost completely protect bindin from inactivation by arginine-specific reagents, butanedione and phenylglyoxal, but only moderately slowed the inactivation by the histidine reagent diethyl pyrocarbonate. In contrast, prior fucan binding could not prevent loss of activity by the reaction of citraconic anhydride with lysine residues. Other sulfated polysaccharides which do not interact strongly with bindin did not protect binding from phenylglyoxal-mediated inactivation when 800-3000-fold more polysaccharide than fucan was used during the preincubation before modification. We found that the larger and more hydrophobic arginine-modifying reagents, camphorquinone-10-sulfonic acid and cyclohexanedione, fail to inactivate fucan binding, suggesting that essential arginine residues may reside in an environment with restricted accessibility to these reagents. Parallel kinetic studies monitoring [14C]phenylglyoxal incorporation and fucan binding inactivation indicate that several of the four total arginine residues may be critical for fucan binding.(ABSTRACT TRUNCATED AT 250 WORDS)

  5. The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

    Directory of Open Access Journals (Sweden)

    M. Ammann

    2008-09-01

    Full Text Available Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3, an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g. The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15, which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12 and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

  6. Real-world healthcare utilization in asthma patients using albuterol sulfate inhalation aerosol (ProAir® HFA with and without integrated dose counters

    Directory of Open Access Journals (Sweden)

    Kerwin EM

    2017-05-01

    Full Text Available Edward M Kerwin,1 Thomas J Ferro,2 Rinat Ariely,3 Debra E Irwin,4 Ruchir Parikh3 1Clinical Trials Division, Clinical Research Institute of Southern Oregon, PC, Medford, OR, 2Global Medical Affairs, 3Global Health Economics and Outcome Research, Teva Pharmaceuticals, Frazer, PA, 4Outcomes Research, Truven Health Analytics, Durham, NC, USA Background: Accurate tracking of the administered dose of asthma rescue inhalers is critical for optimal disease management and is related to reductions in rates of unscheduled health care utilization in asthma patients. There are few published data on the real-world impact of rescue inhalers with integrated dose counters (IDCs on health care resource utilization (HRU for asthma patients. This study evaluates HRU among users of ProAir® hydrofluoroalkane (HFA (albuterol sulfate inhalation aerosol, with IDC versus without IDC, in asthma patients.Methods: This was a retrospective administrative claims study of asthma patients receiving a new prescription for albuterol inhalation aerosol without IDC during 2 years (January 2011–December 2012 or with IDC during the first full year after IDC implementation in the USA (July 2013–July 2014. Six months of continuous enrollment with medical and prescription drug benefits were required before and after the first prescription during the study period. Data on respiratory-related hospitalizations and emergency department (ED visits were collected during the follow-up period.Results: A total of 135,305 (32% patients used albuterol inhalation aerosol with IDC, and 287,243 (68% patients received albuterol inhalation aerosol without IDC. After adjusting for baseline confounding factors, the odds ratio (OR for experiencing a respiratory-related hospitalization (OR=0.92; 95% confidence interval [CI] 0.88–0.96 or ED visit (OR=0.92; 95% CI 0.90–0.94 was significantly lower among patients using albuterol inhalation aerosol with IDC versus without IDC.Conclusion: In a real

  7. Evidence for Acid-Sulfate Alteration in the Pahrump Hills Region, Gale Crater, Mars

    Science.gov (United States)

    Rampe, E. B.; Ming, D. W.; Vaniman, D. T.; Blake, D. F.; Chipera, S.; Morris, R. V.; Bish, D. L.; Cavanagh, P.; Achilles, C.; Bristow, T.; Fairen, A.; Morrison, S. M.; Treiman, A. H.; Crisp, J. A.; Downs, R. T.; Farmer, J. D.; Fendrich, K.; Morookian, J.

    2015-12-01

    The Pahrump Hills region of Gale crater is a ~12 m thick section of sedimentary rock in the Murray formation, interpreted as the basal geological unit of Mount Sharp. The Mars Science Laboratory, Curiosity, arrived at the Pahrump Hills in September 2014 and performed a detailed six-month investigation of the sedimentary structures, geochemistry, and mineralogy of the area. During the campaign, Curiosity drilled and delivered three mudstone samples (targets Confidence Hills, Mojave 2, and Telegraph Peak) to its internal instruments, including the CheMin XRD/XRF. Results from CheMin show that these samples have variable amounts of plagioclase, pyroxene, iron oxides, jarosite, phyllosilicates, cristobalite, and X-ray amorphous material. The presence of jarosite in all samples indicates these rocks were affected by acid-sulfate alteration, and the mineralogical and geochemical trends observed through the section may give more insight into this process. Geochemical data measured by APXS show enrichment in Si and depletion in Mg moving up section. CheMin data show that cristobalite is more abundant up section, whereas pyroxene and phyllosilicates are more abundant at the bottom of the section. Based on mineralogical and geochemical trends and diagenetic features observed in the Pahrump Hills, we hypothesize that the sediments were altered in-situ by acid-sulfate fluids moving down from the top of the section to leach mobile elements, dissolve the minerals most susceptible to acidic alteration, and precipitate secondary silica at the top of the section. Alternative interpretations of the observed mineralogical and geochemical data are possible, including the hypothesis that the redox conditions of the body of water in which the sediments were deposited changed over time.

  8. Higher fecal bile acid hydrophobicity is associated with exacerbation of dextran sodium sulfate colitis in mice.

    Science.gov (United States)

    Stenman, Lotta K; Holma, Reetta; Forsgård, Richard; Gylling, Helena; Korpela, Riitta

    2013-11-01

    Increased luminal bile acid hydrophobicity is associated with cytotoxicity and has been suggested to contribute to gut barrier dysfunction. The aim of this study was to compare 2 high-fat diets and a low-fat diet as to whether they modify fecal bile acid profile and hydrophobicity and/or susceptibility to dextran sodium sulfate (DSS) colitis in C57Bl/6J mice. Control and DSS-Control groups received a low-fat control diet [5.5% of total energy (E%) soy oil, 4.5 E% lard], and the DSS-Lard (5.5 E% soy oil, 54.5 E% lard) and DSS-Fish oil (5.5 E% soy oil, 27.2 E% lard and 27.2% menhaden oil) groups received high-fat diets. Feces for bile acid analysis were collected after 3-wk feeding, followed by induction of dextran DSS colitis (2 d 5% DSS in drinking water + 2 d tap water). Fecal bile acid hydrophobicity was elevated 76% in the lard group (P = 0.051) and 122% in the fish oil group (P = 0.001) compared with control, indicating potentially increased cytotoxicity. DSS caused severe colitis symptoms, evaluated as rectal bleeding, whereas all the controls were symptom free. The median symptom scores were: DSS-Control, 2.3 (IQR = 0.6, 3.0); DSS-Lard, 0.3 (IQR = 0, 2.3); and DSS-Fish oil, 2.4 (IQR = 1.9, 2.8). The only differences were DSS-Control vs. control (P fecal bile acid hydrophobicity (Spearman's ρ = 0.43; P = 0.028) and fecal deoxycholic acid concentration (Spearman's ρ = 0.39; P = 0.048). These results suggest that luminal bile acid modification, induced by altered dietary fat composition, may alter susceptibility to DSS colitis.

  9. Factors Controlling Deoxygenation of "Floodwater" Overlying an Acid Sulfate Soil: Experimental Modeling

    Institute of Scientific and Technical Information of China (English)

    C. LIN; P. G. HASKINS; J. LIN

    2003-01-01

    An incubation experiment was conducted to simulate the effect of flooding on water deoxygenation in acid sulfate soil floodplain systems. The originally oxygenated "floodwater" could be deoxygenated immediately following "flooding" and it is likely that this was caused mainly by decomposition of organic debris from the inundated plants. Deoxygenation eventually led to the depletion of dissolved oxygen (DO) in the "floodwater"and it is highly possible that this resulted in the transformations of ferric Fe to ferrous Fe, sulfate to hydrogen sulfide, and organic nitrogen to ammonia (ammonification). The accumulation of these reduced substances allows the "floodwater" to develop DO-consuming capacity (DOCC). When the "floodwater" is mixed with the introduced oxygenated water, apart from the dilution effects, the reduced substances contained in the "floodwater" oxidize to further consume DO carried by the introduced water. However, it appears that the DO drop in the mixed water can only last for a few hours if no additional DO-depleted "floodwater" is added.Entry of atmospheric oxygen into the water can raise the DO level of the mixed water and lower water pH through the oxidation of the reduced substances.

  10. Water-soluble ions species of size-resolved aerosols: Implications for the atmospheric acidity in São Paulo megacity, Brazil

    Science.gov (United States)

    Vieira-Filho, Marcelo; Pedrotti, Jairo J.; Fornaro, Adalgiza

    2016-11-01

    Over the last decade, an increase of ammonium salts in atmospheric deposition has been reported worldwide, especially in megacities. The present study aims to give a better comprehension analysis about particulate matter acidity in São Paulo megacity (MASP), Brazil. Size-resolved aerosols were sampled in MASP, during 2012 winter, showing a bimodal mass concentration distribution, with sulfate concentration exceeding 3.40 μg m- 3, which accounted for over 25% of PM0.56 mass. Regarding the relative distribution of ionic species, 90% of NH4+ levels, were restricted to smaller than 1 μm diameter range. The average neutralization index for PM < 1 μm was 0.62, which indicated an ammonia-limiting atmosphere due to partial neutralization of atmospheric acids. Particles of the accumulation mode presented more acid behavior than other aerosol fractions, with pH value as low as 4.15 in PM0.56. The total neutralization index registered the lowest value for PM0.56, but it did not respond promptly to aerosol variations as the E-AIM model predictions. The highest discrepancies between the acidity proxies occurred in the smaller fractions of particulate matter, especially in the after-filter (AF) stage (diameter < 0.020 μm). In addition, AF stage had the highest contribution to PM total mass, about 14% for all the stages analyzed. Such contribution indicates that acidity in ultrafine particles are still mixed for the MASP and need further investigation.

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

    Directory of Open Access Journals (Sweden)

    C. M. Pavuluri

    2015-01-01

    Full Text Available 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.

  12. Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

    Science.gov (United States)

    Hammarstrom, J.M.; Seal, R.R.; Meier, A.L.; Kornfeld, J.M.

    2005-01-01

    Weathering of metal-sulfide minerals produces suites of variably soluble efflorescent sulfate salts at a number of localities in the eastern United States. The salts, which are present on mine wastes, tailings piles, and outcrops, include minerals that incorporate heavy metals in solid solution, primarily the highly soluble members of the melanterite, rozenite, epsomite, halotrichite, and copiapite groups. The minerals were identified by a combination of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe. Base-metal salts are rare at these localities, and Cu, Zn, and Co are commonly sequestered as solid solutions within Fe- and Fe-Al sulfate minerals. Salt dissolution affects the surface-water chemistry at abandoned mines that exploited the massive sulfide deposits in the Vermont copper belt, the Mineral district of central Virginia, the Copper Basin (Ducktown) mining district of Tennessee, and where sulfide-bearing metamorphic rocks undisturbed by mining are exposed in Great Smoky Mountains National Park in North Carolina and Tennessee. Dissolution experiments on composite salt samples from three minesites and two outcrops of metamorphic rock showed that, in all cases, the pH of the leachates rapidly declined from 6.9 to 30 mg L-1), Fe (>47 mg L-1), sulfate (>1000 mg L-1), and base metals (>1000 mg L-1 for minesites, and 2 mg L-1 for other sites). Geochemical modeling of surface waters, mine-waste leachates, and salt leachates using PHREEQC software predicted saturation in the observed ochre minerals, but significant concentration by evaporation would be needed to reach saturation in most of the sulfate salts. Periodic surface-water monitoring at Vermont minesites indicated peak annual metal loads during spring runoff. At the Virginia site, where no winter-long snowpack develops, metal loads were highest during summer months when salts were dissolved periodically by rainstorms following sustained evaporation during dry

  13. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and fatty acids: Implications for atmospheric processing of organic aerosols

    Science.gov (United States)

    Zhang, Yan-Lin; Kawamura, Kimitaka; Cao, Fang; Lee, Meehye

    2016-04-01

    Stable carbon isotopic compositions (δ13C) were measured for 23 individual organic species including 9 dicarboxylic acids, 7 oxocarboxylic acids, 1 tricarboxylic acid, 2 α-dicarbonyls, and 4 fatty acids in the aerosols from Gosan background site in East Asia. δ13C values of particle phase glyoxal and methylglyoxal are significantly larger than those previously reported for isoprene and other precursors. The values are consistently less negative in oxalic acid (C2, average -14.1‰), glyoxylic acid (-13.8‰), pyruvic acid (-19.4‰), glyoxal (-13.5‰), and methylglyoxal (-18.6‰) compared to other organic species (e.g., palmitic acid, -26.3‰), which can be explained by the kinetic isotope effects during atmospheric oxidation of pre-aged precursors (e.g., isoprene) and the subsequent gas-particle partitioning after the evaporation of clouds or wet aerosols. The δ13C values of C2 is positively correlated with C2 to organic carbon ratio, indicating that photochemical production of C2 is more pronounced than its degradation during long-range atmospheric transport. The isotopic results also suggest that aqueous phase oxidation of glyoxal and methylglyoxal is a major formation process of oxalic acid via the intermediates such as glyoxylic acid and pyruvic acid. This study provides evidence that organic aerosols are intensively photochemically aged in the western North Pacific rim.

  14. Improved aerosolization performance of salbutamol sulfate formulated with lactose crystallized from binary mixtures of ethanol-acetone.

    Science.gov (United States)

    Kaialy, Waseem; Ticehurst, Martyn D; Murphy, John; Nokhodchi, Ali

    2011-07-01

    It has been shown that dry powder inhaler (DPI) formulations typically achieve low fine particle fractions (poor performance). A commonly held theory is that this is due, at least in part, to low levels of detachment of drug from lactose during aerosolization as a result of strong adhesion of drug particles to the carrier surfaces. Therefore, the purpose of the present study is to overcome poor aerosolization performance of DPI formulation by modification of lactose particles. Lactose particles were crystallized by adding solution in water to different ratios of binary mixtures of ethanol-acetone. The results showed that modified lactose particles had exceptional aerosolization performance that makes them superior to commercial lactose particles. Morphology assessment showed that crystallized lactose particles were less elongated, more irregular in shape, and composed of smaller primary lactose particles compared with commercial lactose. Solid-state characterization showed that commercial lactose particles were α-lactose monohydrate, whereas crystallized lactose particles were a mixture of α-lactose monohydrate and β-lactose according to the ratio of ethanol-acetone used during crystallization process. The enhanced performance could be mainly due to rougher surface and/or higher amounts of fines compared with the lactose crystallized from pure ethanol or commercial lactose. Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association

  15. Effects of Multiple Soil Conditioners on a Mine Site Acid Sulfate Soil for Vetiver Growth

    Institute of Scientific and Technical Information of China (English)

    LIN Chu-Xia; LONG Xin-Xian; XU Song-Jun; CHU Cheng-Xing; MAI Shao-Zhi; JIANG Dian

    2004-01-01

    A pot experiment was conducted to investigate the effects of various soil treatments on the growth of vetiver grass ( Vetiveria zizanioides (L.) Nash) with the objective of formulating appropriate soil media for use in sulfide-bearing mined areas. An acidic mine site acid sulfate soil (pH 2.8) was treated with different soil conditioner formula including hydrated lime, red mud (bauxite residues), zeolitic rock powder, biosolids and a compound fertilizer. Soils treated with red mud and hydrated lime corrected soil acidity and reduced or eliminated metal toxicity enabling the establishment of vetiver grass.Although over-liming affected growth, some seedlings of vetiver survived the initial strong alkaline conditions. Addition of appropriate amounts of zeolitic rock powder also enhanced growth, but over-application caused detrimental effects. In this experiment, soil medium with the best growth performance of vetiver was 50 g of red mud, 10 g of lime, 30 g of zeolitic rock powder and 30 g of biosolids with 2000 g of mine soils (100% survival rate with the greatest biomass and number of new shoots), but adding a chemical fertilizer to this media adversely impacted plant growth. In addition, a high application rate of biosolids resulted in poorer growth of vetiver, compared to a moderate application rate.

  16. Impeded Acidification of Acid Sulfate Soils in an Inter—sively Drained Sugarcane Land

    Institute of Scientific and Technical Information of China (English)

    C.LIN; R.T.BUSH; 等

    2001-01-01

    Recent research results suggest that acidification of acid sulfate soils may be inhibited in well-drained estuarine floodplains in eastern Australia by the absence of natural creek levees,The lack of natural levees has allowed the inuudation of the land by regular tidal flooding prior to the construction of flood mitigation work.Such physiographical conditions prevent the development of pre-draingae pyrite-derived soil acidifica-tion that possibly occurred at many levee-protected sites in eastern Australian estuarine floodplains during extremely dry spells.Pre-drainage acidification is considered as an important condition for accumulation of soluble Fe and consequently,the creation of favourable environments for catalysed pyrite oxidation.Under current intensively drained onditions,the acid materials produced by ongoing pyrite oxidation can be rapidly removed from soil pore water by lateral leaching and acid buffering,resulting in low concentrations of soluble Fe in the pyritic layer,which could reduce the rate of pyrite oxidation.

  17. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

    Energy Technology Data Exchange (ETDEWEB)

    Kirk Nordstrom, D. [US Geological Survey, Boulder, CO 80303 (United States)], E-mail: dkn@usgs.gov; Blaine McCleskey, R.; Ball, James W. [US Geological Survey, Boulder, CO 80303 (United States)

    2009-02-15

    Many waters sampled in Yellowstone National Park, both high-temperature (30-94 deg. C) and low-temperature (0-30 deg. C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H{sub 2}S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <{+-}10%. When the charge imbalance was generally >{+-}10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H{sub 2}S or S{sub 2}O{sub 3} oxidation, CO{sub 2} degassing, and the temperature-dependence of pK{sub 2} for H{sub 2}SO{sub 4}. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO{sub 4} concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high {delta}{sup 18}O values (-10 per mille to -3 per mille ) and a {delta}D vs. {delta}{sup 18}O slope of 3, reflecting kinetic fractionation. Low SO{sub 4} concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl{sup -} concentration increases from boiling which appears inconsistent with the hypothesis of H{sub 2}S oxidation as a source of hydrothermal SO{sub 4}. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and

  18. Effect of the ratio of zinc amino acid complex to zinc sulfate on the performance of Holstein cows

    National Research Council Canada - National Science Library

    Nayeri, A; Upah, N C; Sucu, E; Sanz-Fernandez, M V; DeFrain, J M; Gorden, P J; Baumgard, L H

    2014-01-01

    Multiparous (n=70) and primiparous (n=66) Holstein cows were balanced by 305-d previous mature-equivalent milk yield and parity and assigned to 1 of 3 dietary treatments to evaluate the ratio of zinc sulfate to zinc amino acid complex (CZ...

  19. Effects of folic acid and zinc sulfate on male factor subfertility: a double-blind, randomized, placebo-controlled trial.

    NARCIS (Netherlands)

    Wong, W.Y.; Merkus, J.M.W.M.; Thomas, C.M.G.; Menkveld, R.; Zielhuis, G.A.; Steegers-Theunissen, R.P.M.

    2002-01-01

    OBJECTIVE: To study the effects of folic acid and zinc sulfate treatment on semen variables in fertile and subfertile men. DESIGN: Double-blind, placebo-controlled interventional study. SETTING: Two outpatient fertility clinics and nine midwifery practices in The Netherlands. PARTICIPANT(S): One hun

  20. A missing source of aerosols in Antarctica - beyond long-range transport, phytoplankton, and photochemistry

    Science.gov (United States)

    Giordano, Michael R.; Kalnajs, Lars E.; Avery, Anita; Goetz, J. Douglas; Davis, Sean M.; DeCarlo, Peter F.

    2017-01-01

    . The second phase appears as a transitional phase during the extended polar sunrise. The third phase is marked by an increased importance of biogenically derived sulfate to the total aerosol population (photolysis of dimethyl sulfate and methanesulfonic acid (DMS and MSA)). The increased importance of MSA is identified both through the direct, real-time measurement of aerosol MSA and through the use of positive matrix factorization on the sulfur-containing ions in the high-resolution mass-spectral data. Given the importance of sub-250 nm particles, the aforementioned second phase suggests that early austral spring is the season where new particle formation mechanisms are likely to have the largest contribution to the aerosol population in Antarctica.

  1. Constraining the contribution of organic acids and AMS m/z 44 to the organic aerosol budget: On the importance of meteorology, aerosol hygroscopicity, and region

    OpenAIRE

    2010-01-01

    Geophysical Research Letters, Vol. 37, L21807 The article of record as published may be located at http://dx.doi.org/10.1029/2010GL044951 Airborne measurements in regions of varying meteorology and pollution are used to quantify the contribution of organic acids and a mass spectral marker for oxygenated aerosols, m/z 44, to the total organic aerosol budget. Organic acids and m/z 44 separately are shown to exhibit their highest organic mass fractions in the vicinity of ...

  2. The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

    Science.gov (United States)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-10-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  3. The effect of low solublility organic acids on the hygroscopicity of sodium halide aerosols

    Science.gov (United States)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-02-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be performed in this study. The hygroscopic properties of sodium halide submicrometer particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, Scanning Electron Microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion: whereas the organic covering has little effect in NaBr particles, NaCl and NaI covered particles change their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  4. N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate as a novel, efficient, and reusable solid acid catalyst for acylation under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Nader Ghaffari Khaligh; Parisa Ghods Ghasem-Abadi

    2014-01-01

    N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate has been developed as a recyclable solid acid catalyst for the acetylation of alcohols, phenols, thiols, and amines, as well as the 1,1- diacetyla-tion of aldehydes under solvent-free conditions at room temperature. The acetylated products were formed in good to excellent yields over short reaction times, and the catalyst could be readily re-covered by filtration and used several times without any discernible loss in activity. The hydrogen sulfate anion of the catalytic system was found to play a critical role in enhancing the reaction time and yield of the acetylation reaction.

  5. Viscosity controls humidity dependence of N2O5 uptake to citric acid aerosol

    Science.gov (United States)

    Gržinić, G.; Bartels-Rausch, T.; Berkemeier, T.; Türler, A.; Ammann, M.

    2015-12-01

    The heterogeneous loss of dinitrogen pentoxide (N2O5) to aerosol particles has a significant impact on the night-time nitrogen oxide cycle and therefore the oxidative capacity in the troposphere. Using a 13N short-lived radioactive tracer method, we studied the uptake kinetics of N2O5 on citric acid aerosol particles as a function of relative humidity (RH). The results show that citric acid exhibits lower reactivity than similar dicarboxylic and polycarboxylic acids, with uptake coefficients between ∼ 3 × 10-4-∼ 3 × 10-3 depending on humidity (17-70 % RH). At RH above 50 %, the magnitude and the humidity dependence can be best explained by the viscosity of citric acid as compared to aqueous solutions of simpler organic and inorganic solutes and the variation of viscosity with RH and, hence, diffusivity in the organic matrix. Since the diffusion rates of N2O5 in highly concentrated citric acid solutions are not well established, we present four different parameterizations of N2O5 diffusivity based on the available literature data or estimates for viscosity and diffusivity of H2O. Above 50 % RH, uptake is consistent with the reacto-diffusive kinetic regime whereas below 50 % RH, the uptake coefficient is higher than expected from hydrolysis of N2O5 within the bulk of the particles, and the uptake kinetics is most likely limited by loss on the surface only. This study demonstrates the impact of viscosity in highly oxidized and highly functionalized secondary organic aerosol material on the heterogeneous chemistry of N2O5 and may explain some of the unexpectedly low loss rates to aerosol derived from field studies.

  6. Simulations of sulfate-nitrate-ammonium (SNA) aerosols during the extreme haze events over northern China in October 2014

    Science.gov (United States)

    Chen, Dan; Liu, Zhiquan; Fast, Jerome; Ban, Junmei

    2016-08-01

    Extreme haze events have occurred frequently over China in recent years. Although many studies have investigated the formation mechanisms associated with PM2.5 for heavily polluted regions in China based on observational data, adequately predicting peak PM2.5 concentrations is still challenging for regional air quality models. In this study, we evaluate the performance of one configuration of the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) and use the model to investigate the sensitivity of heterogeneous reactions on simulated peak sulfate, nitrate, and ammonium concentrations in the vicinity of Beijing during four extreme haze episodes in October 2014 over the North China Plain. The highest observed PM2.5 concentration of 469 µg m-3 occurred in Beijing. Comparisons with observations show that the model reproduced the temporal variability in PM2.5 with the highest PM2.5 values on polluted days (defined as days in which observed PM2.5 is greater than 75 µg m-3), but predictions of sulfate, nitrate, and ammonium were too low on days with the highest observed concentrations. Observational data indicate that the sulfur/nitric oxidation rates are strongly correlated with relative humidity during periods of peak PM2.5; however, the model failed to reproduce the highest PM2.5 concentrations due to missing heterogeneous/aqueous reactions. As the parameterizations of those heterogeneous reactions are not well established yet, estimates of SO2-to-H2SO4 and NO2/NO3-to-HNO3 reaction rates that depend on relative humidity were applied, which improved the simulation of sulfate, nitrate, and ammonium enhancement on polluted days in terms of both concentrations and partitioning among those species. Sensitivity simulations showed that the extremely high heterogeneous reaction rates and also higher emission rates than those reported in the emission inventory were likely important factors contributing to those peak PM2.5 concentrations.

  7. Simulations of Sulfate-Nitrate-Ammonium (SNA) aerosols during the extreme haze events over Northern China in 2014

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dan; Liu, Zhiquan; Fast, Jerome D.; Ban, Junmei

    2016-08-30

    Extreme haze events have occurred frequently over China in recent years. Although many studies have investigated the formation mechanisms associated with PM2.5 for heavily polluted regions in China based on observational data, adequately predicting peak PM2.5 concentrations is still challenging for regional air quality models. In this study, we evaluate the performance of one configuration of the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) and use the model to investigate the sensitivity of heterogeneous reactions on simulated peak sulfate, nitrate, and ammonium concentrations in the vicinity of Beijing during four extreme haze episodes in October 2014 over the North China Plain. The highest observed PM2.5 concentration of 469 μg m-3 occurred in Beijing. Comparisons with observations show that the model reproduced the temporal variability in PM2.5 with the highest PM2.5 values on polluted days (defined as days in which observed PM2.5 is greater than 75 μg m-3), but predictions of sulfate, nitrate, and ammonium were too low on days with the highest observed concentrations. Observational data indicate that the sulfur/nitric oxidation rates are strongly correlated with relative humidity during periods of peak PM2.5; however, the model failed to reproduce the highest PM2.5 concentrations due to missing heterogeneous reactions. As the parameterizations of those reactions is not well established yet, estimates of SO2-to-H2SO4 and NO2/NO3-to-HNO3 reaction rates that depend on relative humidity were applied which improved the simulation of sulfate, nitrate, and ammonium enhancement on polluted days in terms of both concentrations and partitioning among those species. Sensitivity simulations showed that the extremely high heterogeneous reaction rates and also higher emission rates than those reported in the emission inventory

  8. Aerosol Disinfection Capacity of Slightly Acidic Hypochlorous Acid Water Towards Newcastle Disease Virus in the Air: An In Vivo Experiment.

    Science.gov (United States)

    Hakim, Hakimullah; Thammakarn, Chanathip; Suguro, Atsushi; Ishida, Yuki; Nakajima, Katsuhiro; Kitazawa, Minori; Takehara, Kazuaki

    2015-12-01

    Existence of bioaerosol contaminants in farms and outbreaks of some infectious organisms with the ability of transmission by air increase the need for enhancement of biosecurity, especially for the application of aerosol disinfectants. Here we selected slightly acidic hypochlorous acid water (SAHW) as a candidate and evaluated its virucidal efficacy toward a virus in the air. Three-day-old conventional chicks were challenged with 25 doses of Newcastle disease live vaccine (B1 strain) by spray with nebulizer (particle size Newcastle disease virus (NDV) strain Sato, too, was immediately inactivated by SAHW containing 50 ppm chlorine in the aqueous phase. These data suggest that SAHW containing 100 ppm chlorine can be used for aerosol disinfection of NDV in farms.

  9. Preparation and Acid Catalytic Activity of TiO2 Grafted Silica MCM-41 with Sulfate Treatment

    Institute of Scientific and Technical Information of China (English)

    Dai-shi Guo; Zi-feng Ma; Chun-sheng Yin; Qi-zhong Jiang

    2008-01-01

    TiO2 grafted silica MCM-41 catalyst with and without sulfate treatment were prepared.The structural and acid properties of these materials were investigated by XRD,N2 adsorption-desorption,element analysis,thermal analysis,Raman and FTIR measurements.Their acid-catalytic activities were evaluated using the cyclization reaction of pseudoionone.It was found that the obtained materials possess well-ordered mesostructure,and the grafted TiO2 components were in highly dispersed amorphous form.T/MCM41 without sulfation contained only Lewis acid sites,while Br(o)nsted and Lewis acidities were remarkably improved for the sulfated materials ST/MCM41 and d-ST/MCM41.T/MCM-41 was not active for the cyclization reaction of pseudoionone,but ST/MCM-41 and d-ST/MCM-41 possessed favorable catalytic activities.The catalytic performance of ST/MCM-41 was comparable with that of the commercial solid acid catalyst of Amberlyst-15,and better than that of d-ST/MCM-41,although the latter underwent a second TiO2 grafting process and accordingly had higher Ti and S content.The specific surface structure of Si-O-Ti-O-S=O in ST/MCM-41 and the bilateral induction effect of Si and S=O on Si-O-Ti bonds were speculated to account for its higher acid catalytic activity.

  10. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan, E-mail: xdy0156@sina.com; Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  11. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Science.gov (United States)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  12. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Science.gov (United States)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  13. Eliminating aluminum toxicity in an acid sulfate soil for rice cultivation using plant growth promoting bacteria.

    Science.gov (United States)

    Panhwar, Qurban Ali; Naher, Umme Aminun; Radziah, Othman; Shamshuddin, Jusop; Razi, Ismail Mohd

    2015-02-20

    Aluminum toxicity is widely considered as the most important limiting factor for plants growing in acid sulfate soils. A study was conducted in laboratory and in field to ameliorate Al toxicity using plant growth promoting bacteria (PGPB), ground magnesium limestone (GML) and ground basalt. Five-day-old rice seedlings were inoculated by Bacillus sp., Stenotrophomonas maltophila, Burkholderia thailandensis and Burkholderia seminalis and grown for 21 days in Hoagland solution (pH 4.0) at various Al concentrations (0, 50 and 100 μM). Toxicity symptoms in root and leaf were studied using scanning electron microscope. In the field, biofertilizer (PGPB), GML and basalt were applied (4 t·ha-1 each). Results showed that Al severely affected the growth of rice. At high concentrations, the root surface was ruptured, leading to cell collapse; however, no damages were observed in the PGPB inoculated seedlings. After 21 days of inoculation, solution pH increased to >6.0, while the control treatment remained same. Field study showed that the highest rice growth and yield were obtained in the bio-fertilizer and GML treatments. This study showed that Al toxicity was reduced by PGPB via production of organic acids that were able to chelate the Al and the production of polysaccharides that increased solution pH. The release of phytohormones further enhanced rice growth that resulted in yield increase.

  14. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    Science.gov (United States)

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu; Chou, Lingjun; Zhuo, Shuping

    2017-07-01

    In this paper, a novel mesoporous sulfated zirconium (M-ZrO2/SO42-) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N2-physisorption and TEM characterization techniques indicated that M-ZrO2/SO42- possessed distinct mesostructure with big specific surface area (133.5 m2 g-1), large pore volume (0.18 cm3 g-1) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO42-, improved the textural properties of prepared materials. In addition, the NH3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO2/SO42- even evacuated at 400 °C. Furthermore, the M-ZrO2/SO42- was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  15. Eliminating Aluminum Toxicity in an Acid Sulfate Soil for Rice Cultivation Using Plant Growth Promoting Bacteria

    Directory of Open Access Journals (Sweden)

    Qurban Ali Panhwar

    2015-02-01

    Full Text Available Aluminum toxicity is widely considered as the most important limiting factor for plants growing in acid sulfate soils. A study was conducted in laboratory and in field to ameliorate Al toxicity using plant growth promoting bacteria (PGPB, ground magnesium limestone (GML and ground basalt. Five-day-old rice seedlings were inoculated by Bacillus sp., Stenotrophomonas maltophila, Burkholderia thailandensis and Burkholderia seminalis and grown for 21 days in Hoagland solution (pH 4.0 at various Al concentrations (0, 50 and 100 μM. Toxicity symptoms in root and leaf were studied using scanning electron microscope. In the field, biofertilizer (PGPB, GML and basalt were applied (4 t·ha−1 each. Results showed that Al severely affected the growth of rice. At high concentrations, the root surface was ruptured, leading to cell collapse; however, no damages were observed in the PGPB inoculated seedlings. After 21 days of inoculation, solution pH increased to >6.0, while the control treatment remained same. Field study showed that the highest rice growth and yield were obtained in the bio-fertilizer and GML treatments. This study showed that Al toxicity was reduced by PGPB via production of organic acids that were able to chelate the Al and the production of polysaccharides that increased solution pH. The release of phytohormones further enhanced rice growth that resulted in yield increase.

  16. Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

    Directory of Open Access Journals (Sweden)

    G. Wang

    2010-07-01

    Full Text Available Dicarboxylic acids (C2–C10, metals, elemental carbon (EC, organic carbon (OC, and stable isotopic compositions of total carbon (TC and total nitrogen (TN were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2 was the dominant diacid, followed by succinic (C4 and malonic (C3 acids. Total diacids in the urban and suburban areas were 1546±203 and 1728±495 ng m−3 during winter and 1236±335 and 1028±193 ng m−3 during spring. EC in the urban and the suburban atmospheres were 17±3.8 and 8.0±2.1 μg m−3 during winter and 20±5.9 and 7.1±2.7 μg m−3 during spring, while OC at the urban and suburban sites were 74±14 and 51±7.9 μg m−3 in winter and 51±20 and 23±6.1 μg m−3 in spring. Secondary organic carbon (SOC accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring were 34±10 and 61±27 μg m−3 in the urban air and 18±7 and 32±23 μg m−3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring was found between primary organic carbon (POC and Ca2+/Fe, together with a strong dependence of pH value of sample extracts on water-soluble inorganic carbon, suggesting fugitive dust as an important source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs, sulfate, and Pb in the samples well correlated each other (r2>0.6 in winter, indicating an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (δ13C became higher with an increase

  17. Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation

    CERN Document Server

    Kirkby, Jasper; Almeida, João; Dunne, Eimear; Duplissy, Jonathan; Ehrhart, Sebastian; Franchin, Alessandro; Gagné, Stéphanie; Ickes, Luisa; Kürten, Andreas; Kupc, Agnieszka; Metzger, Axel; Riccobono, Francesco; Rondo, Linda; Schobesberger, Siegfried; Tsagkogeorgas, Georgios; Wimmer, Daniela; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; David, André; Dommen, Josef; Downard, Andrew; Ehn, Mikael; Flagan, Richard C; Haider, Stefan; Hansel, Armin; Hauser, Daniel; Jud, Werner; Junninen, Heikki; Kreissl, Fabian; Kvashin, Alexander; Laaksonen, Ari; Lehtipalo, Katrianne; Lima, Jorge; Lovejoy, Edward R; Makhmutov, Vladimir; Mathot, Serge; Mikkilä, Jyri; Minginette, Pierre; Mogo, Sandra; Nieminen, Tuomo; Onnela, Antti; Pereira, Paulo; Petäjä, Tuukka; Schnitzhofer, Ralf; Seinfeld, John H; Sipilä, Mikko; Stozhkov, Yuri; Stratmann, Frank; Tomé, Antonio; Vanhanen, Joonas; Viisanen, Yrjo; Vrtala, Aron; Wagner, Paul E; Walther, Hansueli; Weingartner, Ernest; Wex, Heike; Winkler, Paul M; Carslaw, Kenneth S; Worsnop, Douglas R; Baltensperger, Urs; Kulmala, Markku

    2011-01-01

    Atmospheric aerosols exert an important influence on climate1 through their effects on stratiform cloud albedo and lifetime2 and the invigoration of convective storms3. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours4, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small5, 6. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia7. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100–1,000-fold. Time-resolved molecular measurements reveal that n...

  18. Selective cleavage and anticoagulant activity of a sulfated fucan: stereospecific removal of a 2-sulfate ester from the polysaccharide by mild acid hydrolysis, preparation of oligosaccharides, and heparin cofactor II-dependent anticoagulant activity.

    Science.gov (United States)

    Pomin, Vitor H; Pereira, Mariana S; Valente, Ana-Paula; Tollefsen, Douglas M; Pavão, Mauro S G; Mourão, Paulo A S

    2005-04-01

    A linear sulfated fucan with a regular repeating sequence of [3)-alpha-L-Fucp-(2SO4)-(1-->3)-alpha-L-Fucp-(4SO4)-(1-->3)-alpha-L-Fucp-(2,4SO4)-(1-->3)-alpha-L-Fucp-(2SO4)-(1-->]n is an anticoagulant polysaccharide mainly due to thrombin inhibition mediated by heparin cofactor II. No specific enzymatic or chemical method is available for the preparation of tailored oligosaccharides from sulfated fucans. We employ an apparently nonspecific approach to cleave this polysaccharide based on mild hydrolysis with acid. Surprisingly, the linear sulfated fucan was cleaved by mild acid hydrolysis on an ordered sequence. Initially a 2-sulfate ester of the first fucose unit is selectively removed. Thereafter the glycosidic linkage between the nonsulfated fucose residue and the subsequent 4-sulfated residue is preferentially cleaved by acid hydrolysis, forming oligosaccharides with well-defined size. The low-molecular-weight derivatives obtained from the sulfated fucan were employed to determine the requirement for interaction of this polysaccharide with heparin cofactor II and to achieve complete thrombin inhibition. The linear sulfated fucan requires significantly longer chains than mammalian glycosaminoglycans to achieve anticoagulant activity. A slight decrease in the molecular size of the sulfated fucan dramatically reduces its effect on thrombin inactivation mediated by heparin cofactor II. Sulfated fucan with approximately 45 tetrasaccharide repeating units binds to heparin cofactor II but is unable to link efficiently the plasma inhibitor and thrombin. This last effect requires chains with approximately 100 or more tetrasaccharide repeating units. We speculate that the template mechanism may predominate over the allosteric effect in the case of the linear sulfated fucan inactivation of thrombin in the presence of heparin cofactor II.

  19. Antibrowning and antimicrobial properties of sodium acid sulfate in apple slices.

    Science.gov (United States)

    Fan, Xuetong; Sokorai, Kimberly J B; Liao, Ching-Hsing; Cooke, Peter; Zhang, Howard Q

    2009-01-01

    There are few available compounds that can both control browning and enhance microbial safety of fresh-cut fruits. In the present study, the antibrowning ability of sodium acid sulfate (SAS) on "Granny Smith" apple slices was first investigated in terms of optimum concentration and treatment time. In a separate experiment, the apple slices were treated with water or 3% of SAS, calcium ascorbate, citric acid, or acidified calcium sulfate for 5 min. Total plate count, color, firmness, and tissue damage were assessed during a 21-d storage at 4 degrees C. Results showed that the efficacy of SAS in inhibiting browning of apple slices increased with increasing concentration. A minimum 3% of SAS was needed to achieve 14 d of shelf life. Firmness was not significantly affected by SAS at 3% or lower concentrations. Antibrowning potential of SAS was similar for all treatment times ranging from 2 to 10 min. However, SAS caused some skin discoloration of apple slices. When cut surface of apple slices were stained with a fluorescein diacetate solution, tissue damage could be observed under a microscope even though visual damage was not evident. Among the antibrowning agents tested, SAS was the most effective in inhibiting browning and microbial growth for the first 14 d. Total plate count of samples treated with 3% SAS was significantly lower than those treated with calcium ascorbate, a commonly used antibrowning agent. Our results suggested that it is possible to use SAS to control browning while inhibiting the growth of microorganisms on the apple slices if the skin damage can be minimized. Practical Application: Fresh-cut apples have emerged as one of the popular products in restaurants, schools, and food service establishments as more consumers demand fresh, convenient, and nutritious foods. Processing of fresh-cut apples induces mechanical damage to the fruit and exposes apple tissue to air, resulting in the development of undesirable tissue browning. The fresh

  20. Sulfate migration in a river affected by acid mine drainage from the Dabaoshan mining area, South China.

    Science.gov (United States)

    Chen, Meiqin; Lu, Guining; Guo, Chuling; Yang, Chengfang; Wu, Jingxiong; Huang, Weilin; Yee, Nathan; Dang, Zhi

    2015-01-01

    Sulfate, a major component of acid mine drainage (AMD), its migration in an AMD-affected river which located at the Dabaoshan mine area of South China was investigated to pursue the remediation strategy. The existing factors of relatively low pH values of 2.8-3.9, high concentrations of SO4(2-) (∼1940 mg L(-1)) and Fe(3+) (∼112 mg L(-1)) facilitated the precipitation of schwertmannite (Fe8O8(OH)6SO4·nH2O) in the upstream river. Geochemical model calculations implied the river waters were supersaturated, creating the potential for precipitation of iron oxyhydroxides. These minerals evolved from schwertmannite to goethite with the increasing pH from 2.8 to 5.8 along the river. The concentration of heavy metals in river waters was great reduced as a result of precipitation effects. The large size of the exchangeable sulfate pool suggested that the sediments had a strong capacity to bind SO4(2-). The XRD results indicated that schwertmannite was the predominant form of sulfate-bearing mineral phases, which was likely to act as a major sulfate sink by incorporating water-borne sulfate into its internal structure and adsorbing it onto its surface. The small size of reduced sulfur pools and strong oxidative status in the surface sediments further showed that SO4(2-) shifting from water to sediment in form of sulfate reduction was not activated. In short, precipitation of sulfate-rich iron oxyhydroxides and subsequent SO4(2-) adsorption on these minerals as well as water dilution contributed to the attenuation of SO4(2-) along the river waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Evaluating enhanced sulfate reduction and optimized volatile fatty acids (VFA) composition in anaerobic reactor by Fe (III) addition.

    Science.gov (United States)

    Liu, Yiwen; Zhang, Yaobin; Ni, Bing-Jie

    2015-02-17

    Anaerobic reactors with ferric iron addition have been experimentally demonstrated to be able to simultaneously improve sulfate reduction and organic matter degradation during sulfate-containing wastewater treatment. In this work, a mathematical model is developed to evaluate the impact of ferric iron addition on sulfate reduction and organic carbon removal as well as the volatile fatty acids (VFA) composition in anaerobic reactor. The model is successfully calibrated and validated using independent long-term experimental data sets from the anaerobic reactor with Fe (III) addition under different operational conditions. The model satisfactorily describes the sulfate reduction, organic carbon removal and VFA production. Results show Fe (III) addition induces the microbial reduction of Fe (III) by iron reducing bacteria (IRB), which significantly enhances sulfate reduction by sulfate reducing bacteria (SRB) and subsequently changes the VFA composition to acetate-dominating effluent. Simultaneously, the produced Fe (II) from IRB can alleviate the inhibition of undissociated H2S on microorganisms through iron sulfide precipitation, resulting in further improvement of the performance. In addition, the enhancement on reactor performance by Fe (III) is found to be more significantly favored at relatively low organic carbon/SO4(2-) ratio (e.g., 1.0) than at high organic carbon/SO4(2-) ratio (e.g., 4.5). The Fe (III)-based process of this work can be easily integrated with a commonly used strategy for phosphorus recovery, with the produced sulfide being recovered and then deposited into conventional chemical phosphorus removal sludge (FePO4) to achieve FeS precipitation for phosphorus recovery while the required Fe (III) being acquired from the waste ferric sludge of drinking water treatment process, to enable maximum resource recovery/reuse while achieving high-rate sulfate removal.

  2. Dicarboxylic acids, oxoacids, benzoic acid, α-dicarbonyls, WSOC, OC, and ions in spring aerosols from Okinawa Island in the western North Pacific Rim: size distributions and formation processes

    Science.gov (United States)

    Deshmukh, Dhananjay K.; Kawamura, Kimitaka; Lazaar, Manuel; Kunwar, Bhagawati; Boreddy, Suresh K. R.

    2016-04-01

    Size-segregated aerosols (nine stages from 11.3 µm in diameter) were collected at Cape Hedo, Okinawa, in spring 2008 and analyzed for water-soluble diacids (C2-C12), ω-oxoacids (ωC2-ωC9), pyruvic acid, benzoic acid, and α-dicarbonyls (C2-C3) as well as water-soluble organic carbon (WSOC), organic carbon (OC), and major ions (Na+, NH4+, K+, Mg2+, Ca2+, Cl-, NO3-, SO42-, and MSA-). In all the size-segregated aerosols, oxalic acid (C2) was found to be the most abundant species, followed by malonic and succinic acids, whereas glyoxylic acid (ωC2) was the dominant oxoacid and glyoxal (Gly) was more abundant than methylglyoxal. Diacids (C2-C5), ωC2, and Gly as well as WSOC and OC peaked at fine mode (0.65-1.1 µm) whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at coarse mode (3.3-4.7 µm). Sulfate and ammonium were enriched in fine mode, whereas sodium and chloride were in coarse mode. Strong correlations of C2-C5 diacids, ωC2 and Gly with sulfate were observed in fine mode (r = 0.86-0.99), indicating a commonality in their secondary formation. Their significant correlations with liquid water content in fine mode (r = 0.82-0.95) further suggest an importance of the aqueous-phase production in Okinawa aerosols. They may also have been directly emitted from biomass burning in fine mode as supported by strong correlations with potassium (r = 0.85-0.96), which is a tracer of biomass burning. Bimodal size distributions of longer-chain diacid (C9) and oxoacid (ωC9) with a major peak in the coarse mode suggest that they were emitted from the sea surface microlayers and/or produced by heterogeneous oxidation of biogenic unsaturated fatty acids on sea salt particles.

  3. Exchangeable and secondary mineral reactive pools of aluminium in coastal lowland acid sulfate soils.

    Science.gov (United States)

    Yvanes-Giuliani, Yliane A M; Waite, T David; Collins, Richard N

    2014-07-01

    The use of coastal floodplain sulfidic sediments for agricultural activities has resulted in the environmental degradation of many areas worldwide. The generation of acidity and transport of aluminium (Al) and other metals to adjacent aquatic systems are the main causes of adverse effects. Here, a five-step sequential extraction procedure (SEP) was applied to 30 coastal lowland acid sulfate soils (CLASS) from north-eastern New South Wales, Australia. This enabled quantification of the proportion of aluminium present in 'water-soluble', 'exchangeable', 'organically-complexed', 'reducible iron(III) (oxyhydr)oxide/hydroxysulfate-incorporated' and 'amorphous Al mineral' fractions. The first three extractions represented an average of 5% of 'aqua regia' extractable Al and their cumulative concentrations were extremely high, reaching up to 4000 mg·kg(-1). Comparison of Al concentrations in the final two extractions indicated that 'amorphous Al minerals' are quantitatively a much more important sink for the removal of aqueous Al derived from the acidic weathering of these soils than reducible Fe(III) minerals. Correlations were observed between soil pH, dissolved and total organic carbon (DOC and TOC) and Al concentrations in organic carbon-rich CLASS soil horizons. These results suggest that complexation of Al by dissolved organic matter significantly increases soluble Al concentrations at pH values >5.0. As such, present land management practices would benefit with redefinition of an 'optimal' soil from pH ≥5.5 to ~4.8 for the preservation of aquatic environments adjacent to organic-rich CLASS where Al is the sole or principle inorganic contaminant of concern. Furthermore, it was observed that currently-accepted standard procedures (i.e. 1 M KCl extraction) to measure exchangeable Al concentrations in these types of soils severely underestimate exchangeable Al and a more accurate representation may be obtained through the use of 0.2 M CuCl2. Copyright © 2014

  4. Methylsulfonylmethane and boswellic acids versus glucosamine sulfate in the treatment of knee arthritis: Randomized trial.

    Science.gov (United States)

    Notarnicola, Angela; Maccagnano, Giuseppe; Moretti, Lorenzo; Pesce, Vito; Tafuri, Silvio; Fiore, Alessandra; Moretti, Biagio

    2016-03-01

    Until now glucosamine sulfate (GS) has been the most widely used supplement and has been shown to be efficacious in the treatment of osteoarthritis (OA). Methylsulfonylmethane (MSM) and boswellic acids (BA) are new effective supplements for the management of inflammation and joint degeneration, according to previous experimental studies. The aim of our study is to test the effectiveness of association of MSM and BA in comparison with GS in knee arthritis.In this prospective randomized clinical trial, MEBAGA (Methylsulfonylmethane and Boswellic Acids versus Glucosamine sulfate in the treatment of knee Arthritis), 120 participants affected by arthritis of the knee were randomly assigned to an experimental group (MB group) or a control group (GS group) treated for 60 days with 5 g of MSM and 7.2 mg of BA or with 1500 mg of GS daily, respectively. At the 2-month (T1) and 6-months (T2) follow-up , the efficacy of these two nutraceuticals was assessed using the visual analog pain scale (VAS) and the Lequesne Index (LI) for joint function, along with the use of anti-inflammatory drugs (non-steroidal anti-inflammatory drugs and anti-cyclooxygenase-2).The repeated measures ANOVA analysis shows that for VAS, LI, and the use of anti-inflammatory drugs scores there are improvements due to the time in the two groups (respectively, F=26.0; P<0.0001; F=4.15; P=0.02; F=3.38; P=0.04), with a tendency to better values for the MB group at T2.On the basis of these preliminary data, we could support the efficacy of the MSM in association with BA in the treatment of OA. These results are consistent with the anti-inflammatory and chondroprotective effects previously occurred in experimental studies. This new combination of integration (MSM and BS) has presented good results and satisfactory in comparison with GS, until now the cornerstone of the treatment of arthritis in according to guidelines.

  5. Preparation of amino acid nanoparticles at varying saturation conditions in an aerosol flow reactor

    Energy Technology Data Exchange (ETDEWEB)

    Raula, Janne, E-mail: janne.raula@aalto.fi [Aalto University School of Science, Department of Applied Physics (Finland); Lehtimaeki, Matti; Karppinen, Maarit [Aalto University School of Chemical Technology, Department of Chemistry (Finland); Antopolsky, Maxim [University of Helsinki, Drug Discovery and Development Technology Center (Finland); Jiang Hua; Rahikkala, Antti; Kauppinen, Esko I. [Aalto University School of Science, Department of Applied Physics (Finland)

    2012-07-15

    Nanoparticle formation of five amino acids, glycine, l-proline, l-valine, l-phenylalanine, and l-leucine was studied. The aim was to explore factors determining nanoparticle formation and crystallinity. The amino acid nanoparticles have been prepared at different saturation conditions in the aerosol reactor. In a condensed state, the particles were formed by droplet drying. The raise in temperature induced the sublimation of amino acids from the aerosol particles. The amino acid vapor was condensed by physical vapor deposition in a rapid cooling process. The diffusion coefficients and nucleation rates of amino acids have been calculated to understand particle formation. Upon the vapor deposition, amino acids formed crystalline nanoparticles except in the case l-phenylalanine according to X-ray diffraction. The crystal polymorph of glycine in the nanoparticles depended on the applied reactor temperature. The preference of crystallographic orientation varied in both the particle formations from condensed and vapor phase. l-Valine, l-phenylalanine, and l-leucine formed leafy-looking particles. These results could be utilized in the fabrication of nano-sized asperities on drug particle surfaces to reduce forces between particles and accordingly increase particle dispersion in dry powder inhalers.

  6. Assignment of hexuronic acid stereochemistry in synthetic heparan sulfate tetrasaccharides with 2-O-sulfo uronic acids using electron detachment dissociation

    NARCIS (Netherlands)

    Agyekum, Isaac; Patel, Anish B.; Zong, Chengli; Boons, Geert Jan; Amster, I. Jonathan

    2015-01-01

    The present work focuses on the assignment of uronic acid stereochemistry in heparan sulfate (HS) oligomers. The structural elucidation of HS glycosaminoglycans is the subject of considerable importance due to the biological and biomedical significance of this class of carbohydrates. They are highly

  7. Partial replacement of dietary linoleic acid with long chain n-3 polyunsaturated fatty acids protects against dextran sulfate sodium-induced colitis in rats.

    Science.gov (United States)

    Tyagi, Anupama; Kumar, Uday; Santosh, Vadakattu Sai; Reddy, Suryam; Mohammed, Saazida Bhanu; Ibrahim, Ahamed

    2014-12-01

    Imbalances in the dietary n-6 and n-3 polyunsaturated fatty acids have been implicated in the increased prevalence of inflammatory bowel disease. This study investigated the effects of substitution of linoleic acid with long chain n-3 polyunsaturated fatty acids and hence decreasing n-6:n-3 fatty acid ratio on inflammatory response in dextran sulfate sodium induced colitis. Male weanling Sprague Dawley rats were fed diets with n-6:n-3 fatty acid in the ratios of 215,50,10 or 5 for 3 months and colitis was induced by administration of dextran sulfate sodium in drinking water during last 11 days. Decreasing the dietary n-6:n-3 fatty acid ratio to 10 and 5 significantly attenuated the severity of colitis as evidenced by improvements in clinical symptoms, reversal of shortening of colon length, reduced severity of anemia, preservation of colonic architecture as well as reduced colonic mucosal myeloperoxidase activity. This protection was associated with suppression of colonic mucosal proinflammatory mediators such as TNFα, IL-1β and nitric oxide. These findings suggest that long chain n-3 polyunsaturated fatty acids at a level of 3.0 g/kg diet (n-6:n-3 ratio of 10) prevents dextran sulfate sodium induced colitis by suppressing the proinflammatory mediators.

  8. Glycyrrhetic Acid Ameliorates Dextran Sulfate Sodium-Induced Ulcerative Colitis in Vivo

    Directory of Open Access Journals (Sweden)

    Yong-Deok Jeon

    2016-04-01

    Full Text Available Glycyrrhizae Radix (GR is a Korean traditional herb medicine that is widely used in clinical health care. Glycyrrhetic acid (GA is an aglycone saponin extracted from GR that has anti-inflammatory, anti-cancer, and anti-viral effects. However, the anti-inflammatory effects of GA in colitis have not been reported. This study investigated the role of GA on ulcerative colitis in a dextran sulfate sodium (DSS-induced mouse colitis model. DSS-treated mice displayed weight loss and shortened colon length compared with control mice. Mice administered GA showed less weight loss and longer colon length than the DSS-treated group. Interleukin (IL-6, IL-1β, and tumor necrosis factor-alpha were decreased by GA treatment. GA treatment also reduced DSS-induced microscopic damage to colon tissue. GA regulates the phosphorylation of transcription factors including nuclear factor-kappa B (NF-κB and IκB alpha, and regulates the expression of cycloxygenase-2 and prostaglandin E2. GA thus showed beneficial effects in a mouse model of colitis, implicating GA might be a useful herb-derived medicine in the treatment of ulcerative colitis.

  9. Modified ferrous ammonium sulfate benzoic acid xyelenol orange (MFBX) and thermoluminescent dosimeters--a comparative study.

    Science.gov (United States)

    Brindha, S; Rose, J V R; Sathyan, S; Singh I, Rabi Raja; Ravindran, B Paul

    2002-06-07

    Radiation dosimetry deals with the determination of absorbed dose to the medium exposed to ionizing radiation. Chemical dosimetry depends on oxidation or reduction of chemicals by ionizing radiation. A ferrous ammonium sulfate benzoic acid xyelenol orange (FBX) dosimeter based on this principle is being used as a clinical dosimeter at present. Certain modifications were carried out in the preparation and storage of the FBX dosimeter to increase its shelf life. The resulting dosimeter was called a modified FBX (MFBX) dosimeter and has been used in our department for the past few years. An extensive study of the dose, dose rate and energy response of the dosimeter was carried out and compared with a thermoluminescent (LiF7) dosimeter. The results obtained were found to be comparable to the thermoluminescent (LiF7) dosimeter. Hence it was concluded that the MFBX dosimeter could be used for phantom dosimetry, data collection and in vivo measurements. Easier preparation and availability of the reagents are added advantages of using MFBX as a clinical dosimeter in small radiotherapy departments.

  10. Acid and organic aerosol coatings on magnetic nanoparticles increase iron concentrations in human airway epithelial cells.

    Science.gov (United States)

    Ghio, Andrew J; Dailey, Lisa A; Richards, Judy H; Jang, Myoseon

    2009-07-01

    Numerous industrial applications for man-made nanoparticles have been proposed. Interactions of nanoparticles with agents in the atmosphere may impact human health. We tested the postulate that in vitro exposures of respiratory epithelial cells to airborne magnetic nanoparticles (MNP; Fe(3)O(4)) with and without a secondary organic aerosol (SOA) and an inorganic acid could affect iron homeostasis, oxidative stress, and interleukin (IL)-8 release. Cell iron concentrations were increased after exposures to MNP and values were further elevated with co-exposures to either SOA or inorganic acid. Increased expression of ferritin and elevated levels of RNA for DMT1, proteins for iron storage and transport respectively, followed MNP exposures, but values were significant for only those with co-exposures to inorganic acid and organic aerosols. Cell iron concentration corresponded to a measure of oxidative stress in the airway epithelial cells; MNP with co-exposures to SOA and inorganic acid increased both available metal and indices of oxidant generation. Finally, the release of a proinflammatory cytokine (i.e. IL-8) by the exposed cells similarly increased with cell iron concentration. We conclude that MNP can interact with a SOA and an inorganic acid to present metal in a catalytically reactive state to cultured respiratory cells. This produces an oxidative stress to affect a release of IL-8.

  11. Plant and Soil Emissions of Amines and Amino Acids: A Source of Secondary Aerosol Precursors

    Science.gov (United States)

    Jackson, M. L.; Doskey, P. V.; Pypker, T. G.

    2011-12-01

    Ammonia (NH3) is the most abundant alkaline gas in the atmosphere and forms secondary aerosol by neutralizing sulfuric and nitric acids that are released during combustion of fossil fuels. Ammonia is primarily emitted by cropping and livestock operations. However, C2 and C3 amines (pKb 3.3-3.4), which are stronger bases than NH3 (pKb 4.7) have been observed in nuclei mode aerosol that is the precursor to secondary aerosol. Mixtures of amines and amino acids have been identified in diverse environments in aerosol, fog water, cloud water, the soluble fraction of precipitation, and in dew. Glycine (pKb 4.2), serine (pKb 4.8) and alanine (pKb 3.7 and 4.1 for the D and L forms, respectively) are typically the most abundant species. The only reported values of gas-phase glycine, serine and alanine were in marine air and ranged from 6-14 pptv. The origin of atmospheric amines and amino acids has not been fully identified, although sources are likely similar to NH3. Nitrate assimilation in plants forms glycine, serine, and L-alanine, while D-alanine is present in bacterial cell walls. Glycine is converted to serine during C3 plant photorespiration, producing CO2 and NH3. Bacteria metabolize glycine and alanine to methylamine and ethylamine via decarboxylation. Likely sources of amino acids are plants and bacteria, thus concentrations near continental sources are likely greater than those measured in marine air. The overall goal of the research is to examine seasonal variations and relationships between the exchange of CO2, NH3, amines, and amino acids with a corn/soybean rotation in the Midwest Corn Belt. The study presents gaseous profiles of organic amine compounds from various species of vegetation using a mist chamber trapping technique and analysis of the derivatized species by high pressure liquid chromatography with fluorescence detection. Amino acid and amine profiles were obtained for red oak (Quercus rubra), sugar maple (Acer saccharinum), white pine (Pinus

  12. Identification of sulfate reducers and Syntrophobacter sp. in anaerobic granular sludge by fatty-acid biomarkers and 16S rRNA probing

    NARCIS (Netherlands)

    Oude Elferink, S.J.W.H.; Boschker, H.T.S.; Stams, A.J.M.

    1998-01-01

    The sulfate-reducing bacterial sludge population in anaerobic bioreactors, treating different types of wastewater in the presence or absence of sulfate, was evaluated by polar-lipid fatty acid (PLFA) analyses, and by 16S rRNA dot-blot hybridizations using specific 16S rRNA- targeted oligonucleotide

  13. Identification of sulfate reducers and Syntrophobacter sp. in anaerobic granular sludge by fatty-acid biomarkers and 16S rRNA probing

    NARCIS (Netherlands)

    Oude Elferink, S.J.W.H.; Boschker, H.T.S.; Stams, A.J.M.

    1998-01-01

    The sulfate-reducing bacterial sludge population in anaerobic bioreactors, treating different types of wastewater in the presence or absence of sulfate, was evaluated by polar-lipid fatty acid (PLFA) analyses, and by 16S rRNA dot-blot hybridizations using specific 16S rRNA-targeted oligonucleotide p

  14. Identification of sulfate reducers and Syntrophobacter sp. in anaerobic granular sludge by fatty-acid biomarkers and 16S rRNA probing

    NARCIS (Netherlands)

    Oude Elferink, S.J.W.H.; Boschker, H.T.S.; Stams, A.J.M.

    1998-01-01

    The sulfate-reducing bacterial sludge population in anaerobic bioreactors, treating different types of wastewater in the presence or absence of sulfate, was evaluated by polar-lipid fatty acid (PLFA) analyses, and by 16S rRNA dot-blot hybridizations using specific 16S rRNA- targeted oligonucleotide

  15. Identification of sulfate reducers and Syntrophobacter sp. in anaerobic granular sludge by fatty-acid biomarkers and 16S rRNA probing

    NARCIS (Netherlands)

    Oude Elferink, S.J.W.H.; Boschker, H.T.S.; Stams, A.J.M.

    1998-01-01

    The sulfate-reducing bacterial sludge population in anaerobic bioreactors, treating different types of wastewater in the presence or absence of sulfate, was evaluated by polar-lipid fatty acid (PLFA) analyses, and by 16S rRNA dot-blot hybridizations using specific 16S rRNA-targeted oligonucleotide p

  16. SOLUBILITIES AND PHYSICAL PROPERTIES OF SATURATED SOLUTIONS IN THE COPPER SULFATE + SULFURIC ACID + SEAWATER SYSTEM AT DIFFERENT TEMPERATURES

    Directory of Open Access Journals (Sweden)

    F. J. Justel

    2015-09-01

    Full Text Available AbstractIn Chile, the most important economic activity is mining, concentrated in the north of the country. This is a desert region with limited water resources; therefore, the mining sector requires research and identification of alternative sources of water. One alternative is seawater, which can be a substitute of the limited fresh water resources in the region. This work determines the influence of seawater on the solid-liquid equilibrium for acid solutions of copper sulfate at different temperatures (293.15 to 318.15 K, and its effect on physical properties (density, viscosity, and solubility. Knowledge of these properties and solubility data are useful in the leaching process and in the design of copper sulfate pentahydrate crystallization plants from the leaching process using seawater by means of the addition of sulfuric acid.

  17. Ozone-driven daytime formation of secondary organic aerosol containing carboxylic acid groups and alkane groups

    Directory of Open Access Journals (Sweden)

    S. Liu

    2011-08-01

    Full Text Available Carboxylic acids are present in substantial quantities in atmospheric particles, and they play an important role in the physical and chemical properties of aerosol particles. During measurements in coastal California in the summer of 2009, carboxylic acid functional groups were exclusively associated with a fossil fuel combustion factor derived from factor analysis of Fourier transform infrared spectroscopic measurements and closely correlated with oxygenated organic factors from aerosol mass spectrometry measurements. The high fraction of acid groups and the high ratio of oxygen to carbon in this factor suggest that this factor is composed of secondary organic aerosol (SOA products of combustion emissions from the upwind industrial region (the ports of Los Angeles and Long Beach. Another indication of the photochemically-driven secondary formation of this combustion-emitted organic mass (OM was the daytime increase in the concentrations of acid groups and the combustion factors. This daytime increase closely tracked the O3 mixing ratio with a correlation coefficient of 0.7, indicating O3 was closely associated with the SOA maximum and thus likely the oxidant that resulted in acid group formation. Using a pseudo-Lagrangian framework to interpret this daytime increase of carboxylic acid groups and the combustion factors, we estimate that the carboxylic acid groups formed in a 12-h daytime period of one day ("Today's SOA" accounted for 25–33 % of the measured carboxylic acid group mass, while the remaining 67–75 % (of the carboxylic acid group mass was likely formed 1–3 days previously (the "Background SOA". A similar estimate of the daytime increase in the combustion factors suggests that "Today's SOA" and the "Background SOA" respectively contributed 25–50 % and 50–75 % of the combustion factor (the "Total SOA", for a "Total SOA" contribution to the OM of 60 % for the project average. Further, size

  18. SOLUBILITIES AND PHYSICAL PROPERTIES OF SATURATED SOLUTIONS IN THE COPPER SULFATE + SULFURIC ACID + SEAWATER SYSTEM AT DIFFERENT TEMPERATURES

    OpenAIRE

    F. J. Justel; M. Claros; M. E. Taboada

    2015-01-01

    Abstract In Chile, the most important economic activity is mining, concentrated in the north of the country. This is a desert region with limited water resources; therefore, the mining sector requires research and identification of alternative sources of water. One alternative is seawater, which can be a substitute of the limited fresh water resources in the region. This work determines the influence of seawater on the solid-liquid equilibrium for acid solutions of copper sulfate at different...

  19. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, glyoxylic acid and glyoxal in tropical aerosols: implications for photochemical processes of organic aerosols

    Directory of Open Access Journals (Sweden)

    Stelyus L. Mkoma

    2014-10-01

    Full Text Available Tropical aerosols of PM2.5 and PM10 were collected at a rural site in Morogoro, Tanzania (East Africa, and analysed for stable carbon isotopic composition (δ13C of dicarboxylic acids (C2–C9, glyoxylic acid (ωC2 and glyoxal (Gly using gas chromatography/isotope ratio mass spectrometer. PM2.5 samples showed that δ13C of oxalic (C2 acid are largest (mean, −18.3±1.7‰ followed by malonic (C3, −19.6±1.0‰ and succinic (C4, −21.8±2.2‰ acids, whereas those in PM10 are a little smaller: −19.9±3.1‰ (C2, −20.2±2.7‰ (C3 and −23.3±3.2‰ (C4. The δ13C of C2–C4 diacids showed a decreasing trend with an increase in carbon numbers. The higher δ13C values of oxalic acid can be explained by isotopic enrichment of 13C in the remaining C2 due to the atmospheric decomposition of oxalic acid or its precursors. δ13C of ωC2 and Gly that are precursors of oxalic acid also showed larger values (mean, −22.5‰ and −20.2‰, respectively in PM2.5 than those (−26.7‰ and −23.7‰ in PM10. The δ13C values of ωC2 and Gly are smaller than those of C2 in both PM2.5 and PM10. On the other hand, azelaic acid (C9; mean, −28.5‰ is more depleted in 13C, which is consistent with the previous knowledge; that is, C9 is produced by the oxidation of unsaturated fatty acids emitted from terrestrial higher plants. A significant enrichment of 13C in oxalic acid together with its negative correlations with relative abundance of C2 in total diacids and ratios of water-soluble organic carbon and organic carbon further support that a photochemical degradation of oxalic acid occurs during long-range transport from source regions.

  20. Effect of humidity on nitric acid uptake to mineral dust aerosol particles

    Directory of Open Access Journals (Sweden)

    A. Vlasenko

    2006-01-01

    Full Text Available This study presents the first laboratory observation of HNO3 uptake by airborne mineral dust particles. The model aerosols were generated by dry dispersion of Arizona Test Dust (ATD, SiO2, and by nebulizing a saturated solution of calcium carbonate. The uptake of 13N-labeled gaseous nitric acid was observed in a flow reactor on the 0.2–2 s reaction time scale at room temperature and atmospheric pressure. The amount of nitric acid appearing in the aerosol phase at the end of the flow tube was found to be a linear function of the aerosol surface area. SiO2 particles did not show any significant uptake, while the CaCO3 aerosol was found to be more reactive than ATD. Due to the smaller uncertainty associated with the reactive surface area in the case of suspended particles as compared to bulk powder samples, we believe that we provide an improved estimate of the rate of uptake of HNO3 to mineral dust. The fact that the rate of uptake was smaller at a concentration of 1012 than at 1011 was indicative of a complex uptake mechanism. The uptake coefficient averaged over the first 2 s of reaction time at a concentration of 1012 molecules cm-3 was found to increase with increasing relative humidity, from 0.022±0.007 at 12% RH to 0.113±0.017 at 73% RH , which was attributed to an increasing degree of solvation of the more basic minerals. The extended processing of the dust by higher concentrations of HNO3 at 85% RH led to a water soluble coating on the particles and enhanced their hygroscopicity.

  1. The effect of folic acid supplementation with ferrous sulfate on the linear and ponderal growth of children aged 6-24 months: a randomized controlled trial.

    Science.gov (United States)

    Medeiros, D A; Hadler, M C C M; Sugai, A; Torres, V M

    2015-02-01

    Studies evaluating the effect of folic acid supplementation, either alone or in combination with iron, on the linear and ponderal growth of children are practically nonexistent. The aim of this study was to assess the effect of folic acid supplementation with ferrous sulfate on both linear growth and weight gain in anemic and nonanemic children attending Municipal Daycare Centers in Goiania, State of Goias, Brazil. A double-blind, randomized, controlled trial was conducted on 188 children aged 6-24 months. The effects of ferrous sulfate and folic acid supplementation were evaluated using the analysis of variance procedure, based on a double factorial model with two factors of fixed effects (folic acid supplementation and ferrous sulfate supplementation), adjusted for initial weight. The level of significance was 0.05. The children who received folic acid supplementation showed greater weight gain than the monthly average weight gain of those not given the supplement (P=0.026). This effect was independent of the dose of ferrous sulfate (P for interaction=0.693). Folic acid supplementation increased the gain of weight-for-age Z-score when compared with the placebo group (P=0.018), independent of the dose of ferrous sulfate. Folic acid had no effect on linear growth. The use of folic acid supplementation increased the monthly average weight gain and the gain in weight-for-age Z-score compared with the placebo group. This effect was independent of the dose of ferrous sulfate.

  2. Experimental study on effects of boric acid on aerosol revaporization in wind project

    Energy Technology Data Exchange (ETDEWEB)

    Shibazaki, Hiroaki; Maruyama, Yu; Kudo, Tamotsu; Yuchi, Yoko; Chino, Eiichi; Nakamura, Hideo; Hidaka, Akihide; Hashimoto, Kazuichiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2000-11-01

    The revaporization of the once-deposited FPs onto surfaces of reactor coolant piping is being investigated in WIND (Wide Range Piping Integrity Demonstration) project at JAERI. The objectives of the present study are to characterize the aerosol revaporization from piping surfaces under various thermal-hydraulic conditions and to investigate the effects of boric acid on aerosol revaporization. Cesium iodide was introduced into the test section on which metaboric acid was/was not placed in advance. After quantifying the deposited mass of cesium and iodine, the test section was heated to realize the revaporization. The revaporized materials were deposited onto another test section with an axial temperature gradient located in downstream. In the cases that metaboric acid was placed on the test sections, it was found that the mole ratio of iodine to cesium deposited onto wall became gradually small as the wall temperature increased up to 500degC. Chemical analyses with XPS suggested that chemical reaction of deposited cesium iodide with metaboric acid would result in formation of borate, cesium oxide and molecular iodine. In the revaporization phase, the experiments showed that the once-deposited cesium and iodine compounds were mostly revaporized when the temperature exceeded 500degC. (author)

  3. Gallic acid attenuates dextran sulfate sodium-induced experimental colitis in BALB/c mice

    Directory of Open Access Journals (Sweden)

    Pandurangan AK

    2015-07-01

    Full Text Available Ashok Kumar Pandurangan,1,2 Nooshin Mohebali,2 Mohd Esa Norhaizan,1,3 Chung Yeng Looi2 1Department of Nutrition and Dietetics, Faculty of Medicine and Health Sciences, Universiti Putra Malaysia, Serdang, Selangor, Malaysia; 2Department of Pharmacology, Faculty of Medicine, University of Malaya, Kuala Lumpur, Malaysia; 3Laboratory of Molecular Medicine, Institute of Bioscience, Universiti Putra Malaysia, Serdang, Selangor, MalaysiaAbstract: Gallic acid (GA is a polyhydroxy phenolic compound that has been detected in various natural products, such as green tea, strawberries, grapes, bananas, and many other fruits. In inflammatory bowel disease, inflammation is promoted by oxidative stress. GA is a strong antioxidant; thus, we evaluated the cytoprotective and anti-inflammatory role of GA in a dextran sulfate sodium (DSS-induced mouse colitis model. Experimental acute colitis was induced in male BALB/c mice by administering 2.5% DSS in the drinking water for 7 days. The disease activity index; colon weight/length ratio; histopathological analysis; mRNA expressions of IL-21 and IL-23; and protein expression of nuclear erythroid 2-related factor 2 (Nrf2 were compared between the control and experimental mice. The colonic content of malondialdehyde and the activities of superoxide dismutase, catalase, glutathione peroxidase, and glutathione reductase activity were examined as parameters of the redox state. We determined that GA significantly attenuated the disease activity index and colon shortening, and reduced the histopathological evidence of injury. GA also significantly (P<0.05 reduced the expressions of IL-21 and IL-23. Furthermore, GA activates/upregulates the expression of Nrf2 and its downstream targets, including UDP-GT and NQO1, in DSS-induced mice. The findings of this study demonstrate the protective effect of GA on experimental colitis, which is probably due to an antioxidant nature of GA.Keywords: IL-21, NQO1, MDA, enzymic antioxidants

  4. Gaseous Nitrogen Losses from Coastal Acid Sulfate Soils:A Short-Term Study

    Institute of Scientific and Technical Information of China (English)

    B. C. T. MACDONALD; O. T. DENMEAD; I.WHITE; G. BYRANT

    2011-01-01

    NOx and N2O emissions from coastal acid sulfate soils (CASS) cultivated for sugarcane production were investigated on the coastal lowlands of northern New South Wales, Australia. Two series of short-term measurements were made using chambers and micrometeorological techniques. Series 1 occurred during the wet season, the water-filled pore space (WFPS) was between 60%-80% and the site flooded during the measurements. Measurements were made directly after the harvest of soybean crop, which fixed an estimated 100 kg N ha-1, and the emission amounted to 3.2 kg NOx-N ha-1 (12 d) and 1.8 kg N2O-N ha-1 (5 d). Series 2 was made towards the end of the dry season when the WFPS was less than 60%. In Series 2, after an application of 50 kg N ha-1, emissions were markedly less, amounting to 0.9 kg N ha-1 over 10 d. During both series when the soil was moist, emissions of NOx were larger than those of N2O. The emission of NOx appeared to be haphazard, with little time dependence, but there was a clear diurnal cycle for N2O, emphasising the need for continuous measurement procedures for both gases. Theseresults suggest that agricultural production on CASS could be important sources of greenhouse gases and nitrogen practices will need to be optimised to reduce the offsite effects of atmospheric warming, acidification or nitrification. Many questions still remain unanswered such as the emissions during the soybean bean filling stage and crop residue decomposition, the longer-term losses following the fertiliser application and emissions from CASS under different land uses.

  5. Hyaluronic acid-coated cationic nanostructured lipid carriers for oral vincristine sulfate delivery.

    Science.gov (United States)

    Gao, Xuan; Zhang, Jun; Xu, Qiang; Huang, Zun; Wang, Yiyue; Shen, Qi

    2017-04-01

    The goal of this research is to structure a hyaluronic acid modified nanostructured lipid carrier (HA-NLCs) for vincristine sulfate (VCR) delivery, and detect its efficiency to improve the oral bioavailability. Emulsion solvent evaporation method was used to prepare the HA-NLCs nanoparticles. The particle size, zeta potential and entrapment efficiency of VCR-NLCs and HA-NLCs were 187 ± 3.52 nm, -8.61 ± 1.29 mV, 33.12 ± 1.16% and 192 ± 4.41 nm, -32.82 ± 2.64 mV, 34.41 ± 2.21%, respectively. HA-NLCs could significantly improve the cellular uptake efficiency and cytotoxicity in MCF-7 cells than other VCR formulations. The expressions of apoptosis related protein Caspase-3, Caspase-9, Bax and Bcl-2 were estimated by western blot assay in MCF-7 cells, and HA-NLCs exhibited the strongest effect in promoting cell apoptosis. The pharmacokinetics of HA-NLCs was evaluated in Sprague-Dawley male rats and the relative oral bioavailability of HA-NLCs and VCR-NLCs was improved about 1.8-fold and two-fold compared with VCR solution, respectively. Therefore, these results indicated that HA-NLCs could significantly improve the oral bioavailability and was a promising vehicle for the oral delivery of VCR.

  6. Metal and acidity fluxes controlled by precipitation/dissolution cycles of sulfate salts in an anthropogenic mine aquifer

    Science.gov (United States)

    Cánovas, C. R.; Macías, F.; Pérez-López, R.

    2016-05-01

    Underground mine drainages are extremely difficult to study due to the lack of information about the flow path and source proximity in relation to the outflow adit. Geochemical processes controlling metals and acidity fluxes in a complex anthropogenic mine aquifer in SW Spain during the dry and rainy season were investigated by geochemical and statistical tools. High concentrations of acidity, sulfate, metals and metalloids (e.g. Fe, Cu, Zn, As, Cd, Ni, Co) were observed due to intense sulfide oxidation processes. The high residence time inside the anthropogenic aquifer, around 40 days, caused the release of significant quantities of metals linked to host rocks (e.g. Al, Ca, Ge, Li, Mg, REE). The most outstanding characteristic of the acid mine drainage (AMD) outflows is the existence of higher Fe/SO4 molar ratios than those theoretical of pyrite (0.50) during most of the monitored period, due to a fire which occurred in 1949 and remained active for decades. Permanent and temporal retention mechanisms of acidity and metals were observed in the galleries. Once released from sulfide oxidation, Pb and As are sorbed on Fe oxyhydroxysulfate or precipitated as low solubility minerals (i.e. anglesite) inside the galleries. The precipitation of evaporitic sulfate salts during the dry season and the subsequent re-dissolution after rainfall control the fluxes of acidity and main metals (i.e. Fe, Mg, Al) from this anthropogenic aquifer. Some elements, such as Cd, Cu, Ni, REE and Zn, are retained in highly soluble sulfate salts while other elements, such as Ge, Pb and Sc, have a lower response to washout processes due to its incorporation in less soluble sulfate salts. In this way, metal concentration during the washout processes would be controlled by the proportion and solubility of each type of evaporitic sulfate salt stored during the dry season. The recovery of metals of economic interest contained in the AMD could help to self-finance the remediation of these waters in

  7. Aerosol dynamics simulations on the connection of sulphuric acid and new particle formation

    Directory of Open Access Journals (Sweden)

    S.-L. Sihto

    2008-06-01

    Full Text Available We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. We investigated the factors that affect the sulphuric acid dependence during the early stages of particle growth, and tried to find conditions which would yield the linear dependence between the particle number concentration at 3–6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3–6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. The simulations yielded a linear dependence between the particle number concentration at 3 nm and sulphuric acid, when a low saturation vapour pressure for the condensable organic vapour was assumed, or when nucleation took place at ~2 nm instead of ~1 nm. Comparison of results with activation and ternary nucleation showed that ternary nucleation cannot explain the experimentally observed linear or square dependence on sulphuric acid.

  8. Spatial Distribution of Methanesulphonic Acid in the Arctic Aerosol Collected during the Chinese Arctic Research Expedition

    Directory of Open Access Journals (Sweden)

    Peipei Ye

    2015-05-01

    Full Text Available Methanesulphonic acid (MSA, mainly derived from marine biogenic emissions has been frequently used to estimate the marine biogenic contribution. However, there are few reports on MSA over the Arctic Ocean, especially the central Arctic Ocean. Here, we analyzed MSA in aerosol samples collected over the ocean and seas during the Chinese Arctic Research Expedition (CHINARE 2012 using ion chromatography. The aerosol MSA concentrations over the Arctic Ocean varied considerably and ranged from non-detectable (ND to 229 ng/m3, with an average of 27 ± 54 ng/m3 (median: 10 ng/m3. We found the distribution of aerosol MSA exhibited an obvious regional variation, which was affected by biotic and abiotic factors. High values were generally observed in the Norwegian Sea; this phenomenon was attributed to high rates of phytoplankton primary productivity and dimethylsulfide (DMS fluxes in this region. Concentrations over the pack ice region in the central Arctic Ocean were generally lower than over the open waters at the ice edge in the Chukchi Sea. This difference was the mainly caused by sea ice. In addition, we found that higher MSA concentrations were associated with warmer sea surface temperature (SST.

  9. Palmitic Acid on Salt Subphases and in Mixed Monolayers of Cerebrosides: Application to Atmospheric Aerosol Chemistry

    Directory of Open Access Journals (Sweden)

    Ellen M. Adams

    2013-10-01

    Full Text Available Palmitic acid (PA has been found to be a major constituent in marine aerosols, and is commonly used to investigate organic containing atmospheric aerosols, and is therefore used here as a proxy system. Surface pressure-area isotherms (π-A, Brewster angle microscopy (BAM, and vibrational sum frequency generation (VSFG were used to observe a PA monolayer during film compression on subphases of ultrapure water, CaCl2 and MgCl2 aqueous solutions, and artificial seawater (ASW. π-A isotherms indicate that salt subphases alter the phase behavior of PA, and BAM further reveals that a condensation of the monolayer occurs when compared to pure water. VSFG spectra and BAM images show that Mg2+ and Ca2+ induce ordering of the PA acyl chains, and it was determined that the interaction of Mg2+ with the monolayer is weaker than Ca2+. π-A isotherms and BAM were also used to monitor mixed monolayers of PA and cerebroside, a simple glycolipid. Results reveal that PA also has a condensing effect on the cerebroside monolayer. Thermodynamic analysis indicates that attractive interactions between the two components exist; this may be due to hydrogen bonding of the galactose and carbonyl headgroups. BAM images of the collapse structures show that mixed monolayers of PA and cerebroside are miscible at all surface pressures. These results suggest that the surface morphology of organic-coated aerosols is influenced by the chemical composition of the aqueous core and the organic film itself.

  10. Oxalic acid as a heterogeneous ice nucleus in the upper troposphere and its indirect aerosol effect

    Directory of Open Access Journals (Sweden)

    B. Zobrist

    2006-05-01

    Full Text Available Heterogeneous ice freezing points of aqueous solutions containing various immersed solid dicarboxylic acids (oxalic, adipic, succinic, phthalic and fumaric have been measured with a differential scanning calorimeter. The results show that only the dihydrate of oxalic acid (OAD acts as a heterogeneous ice nucleus, with an increase in freezing temperature between 2-5 K depending on solution composition. In several field campaigns, oxalic acid enriched particles have been detected in the upper troposphere with single particle aerosol mass spectrometry. Simulations with a microphysical box model indicate that the presence of OAD may reduce the ice particle number density in cirrus clouds by up to ~50% when compared to exclusively homogeneous cirrus formation without OAD. Using the ECHAM4 climate model we estimate the global net radiative effect caused by this heterogeneous freezing to result in a cooling as high as -0.3 Wm-2.

  11. Bimodal Distribution of Sulfuric Acid Aerosols in the Upper Haze of Venus

    CERN Document Server

    Gao, Peter; Crisp, David; Bardeen, Charles G; Yung, Yuk L

    2013-01-01

    The upper haze (UH) of Venus is variable on the order of days and it is populated by two particle modes. We use a 1D microphysics and vertical transport model based on the Community Aerosol and Radiation Model for Atmospheres to evaluate whether interaction of upwelled cloud particles and sulfuric acid particles nucleated in situ on meteoric dust are able to generate the two size modes and whether their observed variability are due to cloud top vertical transient winds. Nucleation of photochemically produced sulfuric acid onto polysulfur condensation nuclei generates mode 1 cloud droplets that then diffuse upwards into the UH. Droplets generated in the UH from nucleation of sulfuric acid onto meteoric dust coagulate with the upwelled cloud particles and cannot reproduce the observed bimodal size distribution. The mass transport enabled by cloud top transient winds are able to generate a bimodal size distribution in a time scale consistent with observations. Sedimentation and convection in the middle and lower...

  12. Clues on Acid-Sulfate Alteration and Hematite Formation on Earth and Mars From Iron Isotopic Analyses of Terrestrial Analogues From Hawaii

    Science.gov (United States)

    Nie, N. X.; Dauphas, N.; Morris, R. V

    2017-01-01

    The Mars Exploration Rover mission revealed the presence of rocks and minerals indicative of water-rock interactions on Mars. A range of mineralogies have been identified, including hematite spherules (i.e., blueberries), jarosite, Mg-, Ca-sulfates, silica-rich materials and silicate relics from basaltic rocks. The mineral assemblages have been interpreted to be derived from acid-sulfate alteration of basaltic materials. Indeed, the chemical compositions of rocks and soils at Home Plate in Gusev Crater follow the trends expected for acid-sulfate alteration.

  13. Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

    Directory of Open Access Journals (Sweden)

    S.-L. Sihto

    2006-01-01

    Full Text Available We have investigated the formation and early growth of atmospheric secondary aerosol particles building on atmospheric measurements. The measurements were part of the QUEST 2 campaign which took place in spring 2003 in Hyytiälä (Finland. During the campaign numerous aerosol particle formation events occurred of which 15 were accompanied by gaseous sulphuric acid measurements. Our detailed analysis of these 15 events is focussed on nucleation and early growth (to a diameter of 3 nm of fresh particles. It revealed that new particle formation seems to be a function of the gaseous sulphuric acid concentration to the power from one to two when the time delay between the sulphuric acid and particle number concentration is taken into account. From the time delay the growth rates of freshly nucleated particles from 1 nm to 3 nm were determined. The mean growth rate was 1.2 nm/h and it was clearly correlated with the gaseous sulphuric acid concentration. We tested two nucleation mechanisms – recently proposed cluster activation and kinetic type nucleation – as possible candidates to explain the observed dependences, and determined experimental nucleation coefficients. We found that some events are dominated by the activation mechanism and some by the kinetic mechanism. Inferred coefficients for the two nucleation mechanisms are the same order of magnitude as chemical reaction coefficients in the gas phase and they correlate with the product of gaseous sulphuric acid and ammonia concentrations. This indicates that besides gaseous sulphuric acid also ammonia has a role in nucleation.

  14. A new source of oxygenated organic aerosol and oligomers

    Directory of Open Access Journals (Sweden)

    J. Liggio

    2013-03-01

    Full Text Available A large oxygenated organic uptake to aerosols was observed when exposing ambient urban air to inorganic acidic and non-acidic sulfate seed aerosol. For non-acidic seed aerosol the uptake was attributed to the direct dissolution of primary vehicle exhaust gases into the aqueous aerosol fraction, and was correlated to the initial seed sulphate mass. The uptake of primary oxygenated organic gases to aerosols in this study represents a significant amount of organic aerosol (OA that may be considered primary when compared to that reported for primary organic aerosol (POA, but is considerably more oxygenated (O : C ~ 0.3 than traditional POA. Consequently, a fraction of measured ambient oxygenated OA, which correlates with secondary sulphate, may in fact be of a primary, rather than secondary source. These results represent a new source of oxygenated OA on neutral aerosol and imply that the uptake of primary organic gases will occur in the ambient atmosphere, under dilute conditions, and in the presence of pre-existing SO4 aerosols which contain water. Conversely, under acidic seed aerosol conditions, oligomer formation was observed with the uptake of organics being enhanced by a factor of three or more compared to neutral aerosols, and in less than 2 min, representing an additional source of SOA to the atmosphere. This resulted in a trajectory in Van Krevelen space towards higher O : C (slope ~ −1.5, despite a lack of continual gas-phase oxidation in this closed system. The results demonstrate that high molecular weight species will form on acidic aerosols at the ambient level and mixture of organic gases, but are otherwise unaffected by subsequent aerosol neutralization, and that aerosol acidity will affect the organic O : C via aerosol-phase reactions. These two processes, forming oxygenated POA under neutral conditions and SOA under acidic conditions can contribute to the total ambient OA mass and the evolution of ambient aerosol O : C ratios

  15. Cloud droplet activation mechanisms of amino acid aerosol particles: insight from molecular dynamics simulations

    Directory of Open Access Journals (Sweden)

    Xin Li

    2013-07-01

    Full Text Available Atmospheric amino acids constitute a large fraction of water-soluble organic nitrogen compounds in aerosol particles, and have been confirmed as effective cloud condensation nuclei (CCN materials in laboratory experiments. We present a molecular dynamics (MD study of six amino acids with different structures and chemical properties that are relevant to the remote marine atmospheric aerosol–cloud system, with the aim of investigating the detailed mechanism of their induced changes in surface activity and surface tension, which are important properties for cloud drop activation. Distributions and orientations of the amino acid molecules are studied; these l-amino acids are serine (SER, glycine (GLY, alanine (ALA, valine (VAL, methionine (MET and phenylalanine (PHE and are categorised as hydrophilic and amphiphilic according to their affinities to water. The results suggest that the presence of surface-concentrated amphiphilic amino acid molecules give rise to enhanced Lennard–Jones repulsion, which in turn results in decreased surface tension of a planar interface and an increased surface tension of the spherical interface of droplets with diameters below 10 nm. The observed surface tension perturbation for the different amino acids under study not only serves as benchmark for future studies of more complex systems, but also shows that amphiphilic amino acids are surface active. The MD simulations used in this study reproduce experimental results of surface tension measurements for planar interfaces and the method is therefore applicable for spherical interfaces of nano-size for which experimental measurements are not possible to conduct.

  16. Partition of Chiral pharmaceutical intermediate R(-)-Mandelic Acid in Aqueous Two-Phase System of Poly(ethylene glycol)-Ammonium Sulfate

    Institute of Scientific and Technical Information of China (English)

    Xu Xiaoping; Li Zhongqin; Chen Jiebo; Huang Xinghua

    2004-01-01

    An aqueous two-phase system of poly (ethylene glycol)-ammonium sulfate was employed to separate R (-)-mandelic acid.The result showed that R (-)-mandelic acid has priority to partition in PEG-rich top phase. This indicated that aqueous two-phase is a very suitable system for separation of R(-)-mandelic acid.

  17. Evidence for marine biogenic influence on summertime Arctic aerosol

    Science.gov (United States)

    Willis, Megan D.; Köllner, Franziska; Burkart, Julia; Bozem, Heiko; Thomas, Jennie L.; Schneider, Johannes; Aliabadi, Amir A.; Hoor, Peter M.; Schulz, Hannes; Herber, Andreas B.; Leaitch, W. Richard; Abbatt, Jonathan P. D.

    2017-06-01

    We present vertically resolved observations of aerosol composition during pristine summertime Arctic background conditions. The methansulfonic acid (MSA)-to-sulfate ratio peaked near the surface (mean 0.10), indicating a contribution from ocean-derived biogenic sulfur. Similarly, the organic aerosol (OA)-to-sulfate ratio increased toward the surface (mean 2.0). Both MSA-to-sulfate and OA-to-sulfate ratios were significantly correlated with FLEXPART-WRF-predicted air mass residence time over open water, indicating marine-influenced OA. External mixing of sea salt aerosol from a larger number fraction of organic, sulfate, and amine-containing particles, together with low wind speeds (median 4.7 m s-1), suggests a role for secondary organic aerosol formation. Cloud condensation nuclei concentrations were nearly constant (˜120 cm-3) when the OA fraction was <60% and increased to 350 cm-3 when the organic fraction was larger and residence times over open water were longer. Our observations illustrate the importance of marine-influenced OA under Arctic background conditions, which are likely to change as the Arctic transitions to larger areas of open water.

  18. Acidic gases and nitrate and sulfate particles in the atmosphere in the city of Guadalajara, México.

    Science.gov (United States)

    Saldarriaga-Noreña, Hugo; Waliszewski, Stefan; Murillo-Tovar, Mario; Hernández-Mena, Leonel; de la Garza-Rodríguez, Iliana; Colunga-Urbina, Edith; Cuevas-Ordaz, Rosalva

    2012-05-01

    Atmospheric concentrations of nitrous acid, nitric acid, nitrate and sulfate particles were obtained in this study from April to June 2008 in the center of the city of Guadalajara, while concentrations of ozone, sulfur dioxide, nitrogen dioxide and meteorological parameters (temperature and relative humidity), were acquired by the Secretaría del Medio Ambiente para el Desarrollo Sustentable del Estado de Jalisco (SEMADES). The results showed that nitric acid (2.7 μg m(-3)) was 2.7 times higher than nitrous acid (1.0 μg m(-3)). The sulfur dioxide (SO(2)) concentration indicated an opposite trend to sulfate (SO(4) (2-)), with the average concentration of SO(2) (6.9 μg m(-3)) higher in almost the entire period of study. The sulfur conversion ratio (Fs, 24.9%) and nitrogen conversion ratio (Fn, 6.2%), were revealed to be similar to that reported in other urban areas during warm seasons. It is also noted that ozone is not the main oxidizer of nitrogen dioxide and sulfur dioxide. This determination was made by taking into account the slightly positively correlation determined for Fn (r(2) = 0.084) and Fs (r(2) = 0.092) with ozone that perhaps suggests there are other oxidizing species such as the radical OH, which are playing an important role in the processes of atmospheric oxidation in this area.

  19. Heterogeneous conversion of NO2 on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO in the atmosphere?

    Directory of Open Access Journals (Sweden)

    R. Bröske

    2003-01-01

    Full Text Available The heterogeneous conversion of NO2 on different secondary organic aerosols (SOA was investigated with the focus on a possible formation of nitrous acid (HONO. In one set of experiments different organic aerosols were produced in the reactions of O3 with alpha-pinene, limonene or catechol and OH radicals with toluene or limonene, respectively. The aerosols were sampled on filters and exposed to humidified NO2  mixtures under atmospheric conditions. The estimated upper limits for the uptake coefficients of NO2  and the reactive uptake coefficients NO2  -> HONO are in the range of 10-6 and 10-7, respectively. The integrated HONO formation for 1 h reaction time was 13 cm-2 geometrical surface and 17 g-1 particle mass. In a second set of experiments the conversion of NO2 into HONO in the presence of organic particles was carried out in an aerosol flow tube under atmospheric conditions. In this case the aerosols were produced in the reaction of O3 with beta-pinene, limonene or catechol, respectively. The upper limits for the reactive uptake coefficients NO2 -> HONO were in the range of 7 x 10-7 - 9 x 10-6. The results from the present study show that heterogeneous formation of nitrous acid on secondary organic aerosols (SOA is unimportant for the atmosphere.

  20. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    CERN Document Server

    Schobesberger, S; Bianchi, F; Rondo, L; Duplissy, J; Kürten, A; Ortega, I K; Metzger, A; Schnitzhofer, R; Almeida, J; Amorim, A; Dommen, J; Dunne, E M; Ehn, M; Gagné, S; Ickes, L; Junninen, H; Hansel, A; Kerminen, V-M; Kirkby, J; Kupc, A; Laaksonen, A; Lehtipalo, K; Mathot, S; Onnela, A; Petäjä, T; Riccobono, F; Santos, F D; Sipilä, M; Tomé, A; Tsagkogeorgas, G; Viisanen, Y; Wagner, P E; Wimmer, D; Curtius, J; Donahue, N M; Baltensperger, U; Kulmala, M; Worsnop, D R

    2014-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm / Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, in close resemblance to the acid-base bindings ...

  1. Effectiveness of the bran media and bacteria inoculum treatments in increasing pH and reducing sulfur-total of acid sulfate soils

    Science.gov (United States)

    Taufieq, Nur Anny Suryaningsih; Rahim, Sahibin Abdul; Jamil, Habibah

    2013-11-01

    This study was carried out to determine the effectiveness ofsulfate reducing bacteria (SRB) in using bran as a source of food and energy, and to see the effectiveness of the bran media and bacteria inoculums treatments for pH and sulfur-total of acid sulfate reduction insoils. This study used two factors in group random designs with four treatments for bacteria inoculum of B1 (1%), B2 (5%), B3 (10%), B4 (15%) and two treatments for organic media (bran) of D1 (1:1) and D2 (1:19). Based on three replications, the combination resulted in a total of 24 treatments. Soil pH was measured using the Duddridge and Wainright method and determination of sulfate content in soil was conducted by the spectrophotometry method. The data obtained was analyzed for significance by Analysis of Variance and the Least Significant Difference Test. The pH of the initial acid sulfate soils ranged from 3 to 4 and the soil sulfur-total ranged from 1.4% to 10%. After mixing sulfate reducing bacteria with the bran mediaand incubated for four days, the pH of the acid sulfate soils increased from 3.67 to 4.20, while the soil sulfur-total contents had been reduced by 2.85% to 0.35%. This experiment has proven that an acid sulfate soil with low pH is a good growth medium for the sulfate reducing bacteria. The bestincubation period to achieve an effective bioremediation resultthrough sulfate percentage reduction by sulfate reducing bacteria was 10 days, while the optimum bran media dose was 1:19, and the bacteria inoculums dose was 10%.

  2. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study

    Science.gov (United States)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  3. Molecular distributions and isotopic compositions of marine aerosols over the western North Atlantic: Dicarboxylic acids, ketoacids, α-dicarbonyls (glyoxal and methylglyoxal), fatty acids, sugars, and SOA tracers

    Science.gov (United States)

    Kawamura, K.; Ono, K.; Tachibana, E.; Quinn, P.; Bates, T. S.

    2013-12-01

    Marine aerosols were collected over the western North Atlantic from off the coast of Boston to Bermuda during the WACS (Western Atlantic Climate Study) cruise of R/V Ronald H. Brown in August 2012 using a high volume air sampler and pre-combusted quartz fiber filters. Aerosol filter samples (n=5) were analyzed for OC/EC, major inorganic ions, low molecular weight dicarboxylic acids and various secondary organic aerosol (SOA) tracers using carbon analyzer, ion chromatograph, GC/FID and GC/MS, respectively. Homologous series (C2-C12) of dicarboxylic acids (31-335 ng m-3) were detected with a predominance of oxalic acid. Total carbon and nitrogen and their stable isotope ratios were determined as well as stable carbon isotopic compositions of individual diacids using IRMS. Diacids were found to be the most abundant compound class followed by monoterpene-SOA tracers > isoprene-SOA tracers > sugar compounds > ketoacids > fatty alcohols > fatty acids > α-dicarbonyls > aromatic acids > n-alkanes. The concentrations of these compounds were higher in the coastal site and decreased in the open ocean. However, diacids stayed relatively high even in the remote ocean. Interestingly, contributions of oxalic acid to total aerosol carbon increased from the coast (2.3%) to the remote ocean (5.6%) during long-range atmospheric transport. Stable carbon isotopic composition of oxalic acid increased from the coast (-17.5‰) to open ocean (-12.4‰), suggesting that photochemical aging of organic aerosols occurred during the atmospheric transport over the ocean. Stable carbon isotope ratios of bulk aerosol carbon also increased from the coast near Boston to the open ocean near Bermuda.

  4. Electrolytic reduction of U(VI) to U(IV) in acidic chloride and acidic sulfate solutions

    Science.gov (United States)

    Majima, Hiroshi; Awakura, Yasuhiro; Hirono, Shuichiro

    1986-01-01

    In order to examine the applicability of the electrolytic reduction process of U(VI) (originally developed for the chloride system by PNC) to the sulfate solution system, a fundamental study was made. In this study, the concentrations of various chemical species in the catholytes were calculated at 298 K at various percentages of uranium reduction, taking the chloro-complex and sulfato-complex formation reactions of uranium into consideration. The polarization characteristics of the electrolytic reduction of uranyl chloride and uranyl sulfate were determined, using titanium and platinum cathodes, respectively, at 303 ± 1 K. In conjunction with this process, the electrical conductivity of the catholyte, the electrical resistivity of the cation exchange membrane, and the diffusion coefficient of uranyl sulfate were also determined.

  5. Mapping Acid Sulfate Alteration of Basaltic Andesite with Thermal Infrared Data

    Science.gov (United States)

    Vaughan, R. G.; Calvin, W. M.; Hook, S. J.; Taranik, J. V.

    2002-01-01

    Airborne thermal infrared multi- and hyperspectral data sets are used to map sulfate alteration of basaltic andesites near Reno, NV. Alteration includes quartz-alunite, jarosite and a number of clay minerals such as kaolinite and montmorillonite. Additional information is contained in the original extended abstract.

  6. Photochemistry of Glyoxal in Wet Aerosols: Smog Chamber Study

    Science.gov (United States)

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

    2015-12-01

    Aqueous chemistry is an important pathway for the formation of secondary organic aerosol (SOA). Reaction vessel studies provide evidence that in the aqueous phase photooxidation of water soluble organic compounds (e.g., glyoxal, methylglyoxal) form multifunctional organic products and oligomers. In this work, we extend this bulk-phase chemistry to the condensed-phase chemistry that occurs in/on aerosols by conducting smog chamber experiments — photooxidation of ammonium sulfate and sulfuric acid aerosols containing glyoxal and hydrogen peroxide in the presence of NOx under dry/humid conditions. Particles were analyzed using ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). In the irradiated chamber, photooxidation products of glyoxal as seen in reaction vessel experiments (e.g., oxalic acids and tartaric acids) were also formed in both ammonium sulfate aerosols and sulfuric acid aerosols at humid and even dry conditions. However, the major products were organosulfurs (CHOS), organonitrogens (CHON), and nitrooxy-organosulfates (CHONS), which were also dominantly formed in the dark chamber. These products were formed via non-radical reactions, which depend on acidity and humidity. However, the real-time profiles in the dark chamber and the irradiated chamber were very different, suggesting photochemistry substantially affects non-radical formation in the condensed phase.

  7. Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5

    Institute of Scientific and Technical Information of China (English)

    JIANG Ya-jie; JUAN Joon Ching; MENG Xiu-juan; CAO Wei-liang; YARMO Mohd Ambar; ZHANG Jing-chang

    2007-01-01

    Esterification of acrylic acid(AA) to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate(ZS) loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20%(mass fraction) ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.

  8. Characterization of specific membrane fatty acids as chemotaxonomic markers for sulfate-reducing bacteria involved in anaerobic oxidation of methane

    DEFF Research Database (Denmark)

    Elvert, M.; Boetius, A.; Knittel, K.

    2003-01-01

    into bacterial biomass is indicated by carbon isotope values of specific fatty acids as low as -103parts per thousand. Specific fatty acids released from bacterial membranes include C(16:1omega5c) , C(17:1omega6c) , and cyC(17:0omega5,6) , all of which have been fully characterized by mass spectrometry....... These unusual fatty acids continuously display the lowest delta (13)C values in all sediment horizons and two of them are detected in high abundance (i.e., C(16:1omega5c) and cyC(17:0omega5,6) ). Combined with microscopic examination by fluorescence in situ hybridization specifically targeting sulfate...

  9. Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols: implications for photochemical production and degradation in smoke layers

    Directory of Open Access Journals (Sweden)

    A. Hoffer

    2010-03-01

    Full Text Available Aerosols in the size class <2.5 μm (6 daytime and 9 nighttime samples were collected at a pasture site in Rondônia, Brazil, during the intensive biomass burning period of 16–26 September 2002 as part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC. Homologous series of dicarboxylic acids (C2–C11 and related compounds (ketocarboxylic acids and α-dicarbonyls were identified using gas chromatography (GC and GC/mass spectrometry (GC/MS. Among the species detected, oxalic acid was found to be the most abundant, followed by succinic, malonic and glyoxylic acids. Average concentrations of total dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the aerosol samples were 2180, 167 and 56 ng m−3, respectively. These are 2–8, 3–11 and 2–16 times higher, respectively, than those reported in urban aerosols, such as in 14 Chinese megacities. Higher ratios of dicarboxylic acids and related compounds to biomass burning tracers (levoglucosan and K+ were found in the daytime than in the nighttime, suggesting the importance of photochemical production. On the other hand, higher ratios of oxalic acid to other dicarboxylic acids and related compounds normalized to biomass burning tracers (levoglucosan and K+ in the daytime provide evidence for the possible degradation of dicarboxylic acids (≥C3 in this smoke-polluted environment. Assuming that these and related compounds are photo-chemically oxidized to oxalic acid in the daytime, and given their linear relationship, they could account for, on average, 77% of the formation of oxalic acid. The remaining portion of oxalic acid may have been directly emitted from biomass burning as suggested by a good correlation with the biomass burning tracers (K+, CO and ECa and organic carbon (OC. However, photochemical production from other precursors could not be excluded.

  10. Germination and Seedling Growth of Perennial Ryegrass in Acid Sulfate Soil Treated by Pyrite Nano-Encapsulation

    Science.gov (United States)

    Lee, J.; Kim, J.; Yi, J.; Kim, T.

    2007-05-01

    The trial pot experiment was conducted to validate the effect of encapsulation in reduction of acid rock drainage. Six different treatments were performed: A = control, four times spraying of distilled water; B = four times of 0.01 M H2O2; C = once-encapsulated and three times spraying of distilled water; D = twice-encapsulated and twice spraying of distilled water; E = three times-encapsulated and once spraying of distilled water and F = four times-encapsulated for the acid sulfate soil with pyrite bearing andesite powder and sand. After the encapsulation treatment, the perennial ryegrass (Loium perenne) was sowed to evaluate germination rate and growth for three months. The leachate was examined for the chemical properties. The leachate from the A pot (control) is characterized as acidic (pH below 3) and high concentrations of SO4-2: 12,022 mg/L, Al: 85.8 mg/L and Mn: 34.1 mg/L which can be toxic effect to the plant growth. However, the leachate from encapsulated pots showed near neutral (pH 6 to 7) and low concentrations of SO4-2 (below 3,000 mg/L), Al (below 45mg/L) and Mn (24 gm/L). The frequency of encapsulation treatment is related to reduction of acidic drainage. It was hard to identify the significant difference of the seed germination rate of ryegrass between the treatments, although root and shoot growth showed three times difference between the control (1.90g/pot) and four times encapsulated treatment (6.33g/pot) after 2 month growth. It is suggested that encapsulation of pyrite in acid sulfate soil causes the reduction of acidic drainage resulting in the higher growth of herbaceous plants.

  11. Quantifying heavy metals sequestration by sulfate-reducing bacteria in an acid mine drainage-contaminated wetland

    Directory of Open Access Journals (Sweden)

    John W Moreau

    2013-03-01

    Full Text Available Bioremediation strategies that depend on bacterial sulfate reduction for heavy metals remediation harness the reactivity of these metals with biogenic aqueous sulfide. Quantitative knowledge of the degree to which specific toxic metals are partitioned into various sulfide, oxide, or other phases is important for predicting the long-term mobility of these metals under environmental conditions. Here we report the quantitative partitioning into sedimentary biogenic sulfides of a suite of metals and metalloids associated with acid mine drainage contamination of a natural estuarine wetland for over a century.

  12. Quantifying heavy metals sequestration by sulfate-reducing bacteria in an Acid mine drainage-contaminated natural wetland.

    Science.gov (United States)

    Moreau, John W; Fournelle, John H; Banfield, Jillian F

    2013-01-01

    Bioremediation strategies that depend on bacterial sulfate reduction for heavy metals remediation harness the reactivity of these metals with biogenic aqueous sulfide. Quantitative knowledge of the degree to which specific toxic metals are partitioned into various sulfide, oxide, or other phases is important for predicting the long-term mobility of these metals under environmental conditions. Here we report the quantitative partitioning into sedimentary biogenic sulfides of a suite of metals and metalloids associated with acid mine drainage contamination of a natural estuarine wetland for over a century.

  13. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    Science.gov (United States)

    Ranney, April P; Ziemann, Paul J

    2016-04-28

    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be water. The results indicate that HNO3 was only weakly dissociated in the SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed.

  14. Diurnal variations of total carbon, dicarboxylic acids, ketoacids and α-dicarbonyls in aerosols in the northern vicinity of Beijing

    Science.gov (United States)

    He, N.; Kawamura, K.; Okuzawa, K.; Kanaya, Y.; Wang, Z. F.

    2013-06-01

    Aerosol samples (TSP, n=58) were collected on day- and night-time basis at Mangshan in the north of Beijing, China in autumn 2007 to better understand the status of air quality and the influence of urban pollutants in the northern vicinity of Beijing. The samples were analyzed for aerosol mass, total carbon (TC), low molecular weight α, ω-dicarboxylic acids (C2-C12), ketoacids (ωC2-ωC9, pyruvic acid), α-dicarbonyls (glyoxal and methylglyoxal), as well as aromatic (phthalic, iso- and tere-phthalic) diacids. Aerosol mass and TC concentrations are higher in daytime than in nighttime. TC/aerosol mass ratios in this study are lower than those reported in megacities in East Asia, but higher than those reported in marine aerosols. Molecular distributions of diacids demonstrated that oxalic (C2) acid was the most abundant species, comprising 38-77% of total diacids, followed by succinic (C4) and malonic (C3) acids. For most compounds, the concentrations were higher in daytime than nighttime, indicating that diacids are produced in daytime by photochemical oxidation of organic precursors emitted from anthropogenic sources in Beijing during the transport to Mangshan area by the northward wind. However, we found that C2 concentrations are higher in nighttime than in daytime. A positive correlation of C2 to glyoxylic acid (ωC2) was obtained at night when relative humidity increased up to 100%, suggesting that aqueous phase production of C2 occurs in nighttime via the oxidation of ωC2. Depletion of C2 by photolysis of Fe-oxalato complexes might be another reason for the lower concentrations of C2 in daytime samples. High phthalic acid/C4 ratios in the aerosol samples suggest that automobile combustion and coal burning products are important sources, which are subjected to photochemical oxidation during the atmospheric transport of urban aerosols from Beijing. In contrast, higher concentrations of methylglyoxal in nighttime than daytime may suggest that isoprene emitted

  15. Diurnal variations of total carbon, dicarboxylic acids, ketoacids and α-dicarbonyls in aerosols in the northern vicinity of Beijing

    Directory of Open Access Journals (Sweden)

    N. He

    2013-06-01

    Full Text Available Aerosol samples (TSP, n=58 were collected on day- and night-time basis at Mangshan in the north of Beijing, China in autumn 2007 to better understand the status of air quality and the influence of urban pollutants in the northern vicinity of Beijing. The samples were analyzed for aerosol mass, total carbon (TC, low molecular weight α, ω-dicarboxylic acids (C2-C12, ketoacids (ωC2-ωC9, pyruvic acid, α-dicarbonyls (glyoxal and methylglyoxal, as well as aromatic (phthalic, iso- and tere-phthalic diacids. Aerosol mass and TC concentrations are higher in daytime than in nighttime. TC/aerosol mass ratios in this study are lower than those reported in megacities in East Asia, but higher than those reported in marine aerosols. Molecular distributions of diacids demonstrated that oxalic (C2 acid was the most abundant species, comprising 38–77% of total diacids, followed by succinic (C4 and malonic (C3 acids. For most compounds, the concentrations were higher in daytime than nighttime, indicating that diacids are produced in daytime by photochemical oxidation of organic precursors emitted from anthropogenic sources in Beijing during the transport to Mangshan area by the northward wind. However, we found that C2 concentrations are higher in nighttime than in daytime. A positive correlation of C2 to glyoxylic acid (ωC2 was obtained at night when relative humidity increased up to 100%, suggesting that aqueous phase production of C2 occurs in nighttime via the oxidation of ωC2. Depletion of C2 by photolysis of Fe-oxalato complexes might be another reason for the lower concentrations of C2 in daytime samples. High phthalic acid/C4 ratios in the aerosol samples suggest that automobile combustion and coal burning products are important sources, which are subjected to photochemical oxidation during the atmospheric transport of urban aerosols from Beijing. In contrast, higher concentrations of methylglyoxal in nighttime than daytime may suggest that

  16. Direct radiative effect by multicomponent aerosol over China

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xin; Song, Yu; Zhao, Chun; Cai, Xuhui; Zhang, Hongsheng; Zhu, Tong

    2015-05-01

    The direct radiative effect (DRE) of multiple aerosol species (sulfate, nitrate, ammonium, black carbon (BC), organic carbon (OC), and mineral aerosol) and their spatiotemporal variations over China were investigated using a fully coupled meteorology–chemistry model (WRF-Chem) for the entire year of 2006. We made modifications to improve model performance, including updating land surface parameters, improving the calculation of transition metal-catalyzed oxidation of SO2, and adding in heterogeneous reactions between mineral aerosol and acid gases. The modified model well reproduced the magnitude, seasonal pattern, and spatial distribution of the measured meteorological conditions, concentrations of PM10 and its components, and aerosol optical depth (AOD). A diagnostic iteration method was used to estimate the overall DRE of aerosols and contributions from different components. At the land surface, all kinds of aerosol species reduced the incident net radiation flux with a total DRE of 10.2 W m-2 over China. Aerosols significantly warm the atmosphere with the national mean DRE of +10.8 W m-2. BC was the leading radiative-heating component (+8.7 W m-2), followed by mineral aerosol (+1.1 W m-2). At the top of the atmosphere (TOA), BC introduced the largest radiative perturbation (+4.5 W m-2), followed by sulfate (-1.4 W m-2). The overall perturbation of aerosols on radiation transfer is quite small over China, demonstrating the counterbalancing effect between scattering and adsorbing aerosols. Aerosol DRE at the TOA had distinct seasonality, generally with a summer maximum and winter minimum, mainly determined by mass loadings, hygroscopic growth, and incident radiation flux.

  17. Alteration of chemical behavior of L-ascorbic acid in combination with nickel sulfate at different pH solutions in vitro

    Institute of Scientific and Technical Information of China (English)

    Shaheen A Maniyar; Jameel G Jargar; Swastika N Das; Salim A Dhundasi; Kusal K Das

    2012-01-01

    Objective: To evaluate the alteration of chemical behavior of L-ascorbic acid (vitamin C) with metal ion (nickel) at different pH solutions in vitro. Methods: Spectra of pure aqueous solution of L-ascorbic acid (E mark) compound and NiSO4 (H2O) (sigma USA) were evaluated by UV visible spectrophotometer. Spectral analysis of L-ascorbic acid and nickel at various pH (2.0, 7.0, 7.4 and 8.6) at room temperature of 29℃ was recorded. In this special analysis, combined solution of L-ascorbic acid and nickel sulfate at different pH was also recorded. Results: The result revealed that λmax (peak wavelength of spectra) of L-ascorbic acid at pH 2.0 was 289.0 nm whereas at neutral pH 7.0, λmax was 295.4 nm. In alkaline pH 8.6, λmax was 295.4 nm and at pH 7.4 the λmax of L-ascorbic acid remained the same as 295.4 nm. Nickel solution at acidic pH 2.0 was 394.5 nm, whereas at neutral pH 7.0 and pH 7.4 were the same as 394.5 nm. But at alkaline pH 8.6, λmax value of nickel sulfate became 392.0 nm. The combined solution of L-ascorbic acid and nickel sulfate (6 mg/mL each) at pH 2.0 showed 292.5 nm and 392.5 nm, respectively whereas at pH 7.0, L-ascorbic acid showed 296.5 nm and nickel sulfate showed 391.5 nm. At pH 7.4, L-ascorbic acid showed 297.0 nm and nickel sulfate showed 394.0 nm in the combined solution whereas at pH 8.6 (alkaline) L-ascorbic acid and nickel sulfate were showing 297.0 and 393.5 nm, respectively.Conclusions:alone or in combination with nickel sulfate in vitro at different pH. Perhaps oxidation of L-ascorbic acid to L-dehydro ascorbic acid via the free radical (HSc*) generation from the reaction of H2ASc+ Ni (II) is the cause of such alteration of λmax value of L-ascorbic acid in the presence of metal Results clearly indicate an altered chemical behavior of L-ascorbic acid either nickel.

  18. submitter On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

    CERN Document Server

    Schobesberger, S; Bianchi, F; Rondo, L; Duplissy, J; Kürten, A; Ortega, I K; Metzger, A; Schnitzhofer, R; Almeida, J; Amorim, A; Dommen, J; Dunne, E M; Ehn, M; Gagné, S; Ickes, L; Junninen, H; Hansel, A; Kerminen, V -M; Kirkby, J; Kupc, A; Laaksonen, A; Lehtipalo, K; Mathot, S; Onnela, A; Petäjä, T; Riccobono, F; Santos, F D; Sipilä, M; Tomé, A; Tsagkogeorgas, G; Viisanen, Y; Wagner, P E; Wimmer, D; Curtius, J; Donahue, N M; Baltensperger, U; Kulmala, M; Worsnop, D R

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia $(NH_3)$ and sulfuric acid $(H-2SO_4)$. Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small $NH_3–H_2SO_4$ clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high $[NH_3]$ / $[H_2SO_4]$. The $H_2SO_4$ molecules of these clusters are partially neutralized by $NH_3$, in close resemblance...

  19. Methylprednisolone Inhibits the Expression of Glial Fibrillary Acidic Protein and Chondroitin Sulfate Proteoglycans in Reactivated Astrocytes

    Institute of Scientific and Technical Information of China (English)

    WEI-LIN LIU; YI-HSUAN LEE; SHIH-YING TSAI; CHUNG YI HSU; YU-YO SUN; LIANG-YO YANG; SHING-HAN TSAI; WEI-CHUNG VIVIAN YANG

    2008-01-01

    创伤后的神经胶质增生导致硫酸软骨素蛋白聚糖(CSPG)的显著表达,从而抑制轴突生长和再生.甲基强地松龙(MP),一种合成的糖皮质激素,在急性脊髓损伤(SCI)的治疗中有神经保护作用和抗炎效应.但是,MP对于CSPG在活性胶质细胞中的表达的作用尚不清楚.本文用a-氨基-3-羟基-5-甲基-4-异恶唑丙酸酯(AM-PA)诱导星形胶质细胞再活化,用环噻嗪模拟SCI的兴奋性中毒刺激.AMPA治疗后,星形胶质细胞再活化的标志物-胶质纤维酸性蛋白(GFAP)、CSPG神经聚糖和磷酸盐的表达都显著上调.AMPA治疗星形胶质细胞的条件培养液强烈抑制大鼠背根神经节中神经元的轴突生长,但这种作用能被MP的预处理所逆转.此外,MP下调成年SCI大鼠中GFAP和CSPG的表达,对抗RU486的糖皮质激素受体(GR)和GR siRNA能逆转MP对GFAP和神经聚糖表达的抑制作用.这些结果提示,MP能在兴奋性中毒损伤后通过GR介导的星形胶质细胞再活化下调和GSPG表达抑制来改善神经修复,促进轴突生长.%Reactive gliosis caused by post-traumatic injury often results in marked expression of chondroitin sul-fate proteoglycan(CSPG), which inhibits neurite outgrowth and regeneration. Methylprednisolone (MP), a synthet-ic glucocorticoid, has been shown to have neuroprotective and anti-inflammatory effects for the treatment of acute spinal cord injury (SCI). However, the effect of MP on CSPG expression in reactive glial cells remains unclear. In our study, we induced astrocyte reactivation using a-amino-3-hydroxy-5-methyl-4-isoxazole propionate (AMPA) and cyclothiazide to mimic the exciotoxic stimuli of SCI. The expression of glial fibrillary acidic protein (GFAP), a marker of astrocyte reactivation, and CSPG neurocan and phosphacan were significantly elevated by AMPA treat-ment. The conditioned media from AMPA-treated astrocytes strongly inhibited neurite outgrowth of rat dorsal root ganglion neurons, and this

  20. Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

    Science.gov (United States)

    Niles, Paul B.; Golden, D. C.; Michalski, J.

    2013-01-01

    High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial

  1. Thermal stability and surface acidity of mesoporous silica doubly doped by incorporation of sulfate and zirconium ions

    Energy Technology Data Exchange (ETDEWEB)

    Salas, P. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D.F. (Mexico)]. E-mail: psalas@imp.mx; Chen, L.F. [Departamento de Ingenieria Quimica, Universidad Autonoma Metropolitana-A, Av. San Pablo 180, Col. Reynosa-Tamaulipas, 02200 Mexico D.F. (Mexico); Wang, J.A. [Laboratorio de Catalisis y Materiales, ESIQIE, Instituto Politecnico Nacional, Col. Zacatenco, 07738 Mexico D.F. (Mexico); Armendariz, H. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D.F. (Mexico); Guzman, M.L. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D.F. (Mexico); Montoya, J.A. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D.F. (Mexico); Acosta, D.R. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, A. P. 20-364, 01000 Mexico D.F. (Mexico)

    2005-11-15

    A sulfated Si-Zr-MCM-41 solid with highly ordered mesostructure was synthesized through a templated synthesis route where the CTAB surfactant was used as template. During the synthesis procedure, various amounts of (NH{sub 4}){sub 2}SO{sub 4} were added into the mixed solution of Zr and Si precursors to in situ sulfate the MCM-41 solids, aiming to enhance the acidity and thermal stability. The resultant materials showed a long-range ordered hexagonal arrangement with high surface area larger than 797 m{sup 2}/g and an average pore size distributed at approximate 2.5-2.8 nm. The high-resolution TEM observations confirmed that the order of the mesostructure gained when the molar ratio of SO{sub 4} {sup 2-}/(ZrO{sub 2} + SiO{sub 2}) increased from 0.1 to 0.3 but decreased as it reached 0.5, which is consistent with the results of {sup 29}Si MAS-NMR and XRD analysis. Compared to Si-MCM-41, the (Q{sup 2} + Q{sup 3})/Q{sup 4} ratio derived from the NMR spectra of the Zr-doped sample was higher, indicating that zirconium atoms were incorporated into the silica framework. Unexpectedly, in situ sulfation does not enhance the surface Broensted acidity, most likely due to the sulfur retained within the bulk of the materials; however, it indeed improved the thermal stability of the solid and long-range order of the structure.

  2. Synthesis and characterization of sulfated TiO2 nanorods and ZrO2/TiO2 nanocomposites for the esterification of biobased organic acid.

    Science.gov (United States)

    Li, Zhonglai; Wnetrzak, Renata; Kwapinski, Witold; Leahy, James J

    2012-09-26

    TiO(2) nanorods and ZrO(2)-modified TiO(2) nanocomposites have been prepared by hydrothermal synthesis and the deposition-precipitation method. Their sulfated products were tested as solid superacid catalysts for the esterification of levulinic acid which was used as a model bio-oil molecule. SEM and TEM characterization showed that TiO(2) nanorods with diameters ranging from 20 to 200 nm and with lengths of up to 5 μm were synthesized by a hydrothermal method at 180 °C. ZrO(2) nanoparticles with the diameters ranging from 10 to 20 nm were evenly deposited on TiO(2) nanorods. IR and XPS results suggested that sulfated ZrO(2)/TiO(2) nanocomposite has higher content of sulfate groups on the surface with a S/(Zr+Ti) ratio of 13.6% than sulfated TiO(2) nanorods with a S/Ti ratio of 4.9%. The HPLC results showed that sulfated ZrO(2)/TiO(2) nanocomposite have enhanced catalytic activity for esterification reaction between levulinic acid and ethanol compared to sulfated TiO(2) nanorods. The conversion of levulinic acid to ethyl levulinate can reach to 90.4% at the reaction temperature of 105 °C after 180 min.

  3. Atmospheric oxalic acid and related secondary organic aerosols in Qinghai Lake, a continental background site in Tibet Plateau

    Science.gov (United States)

    Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Cao, Junji

    2013-11-01

    Summertime PM2.5 aerosols collected from Qinghai Lake (3200 m a.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2-C11), ketocarboxylic acids and α-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231 ± 119 ng m-3), ketocarboxylic acids (8.4 ± 4.3 ng m-3), and α-dicarbonyls (2.7 ± 2.1 ng m-3) at the Tibetan background site are 2-5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30-400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and α-dicarbonyls at this background site.

  4. Enrichment of sulfate-reducing bacteria and resulting mineral formation in media mimicking pore water metal ion concentrations and pH conditions of acidic pit lakes.

    Science.gov (United States)

    Meier, Jutta; Piva, Angela; Fortin, Danielle

    2012-01-01

    Acid mine drainage sites are extreme environments with high acidity and metal ion concentrations. Under anoxic conditions, microbial sulfate reduction may trigger the formation of secondary minerals as a result of H2S production and pH increase. This process was studied in batch experiments with enrichment cultures from acidic sediments of a pit lake using growth media set at different pH values and containing elevated concentrations of Fe²⁺ and Al³⁺. At initial pH values of 5 and 6, sulfate reduction occurred shortly after inoculation. Sulfate- reducing bacteria affiliated to the genus Desulfosporosinus predominated the microbial communities as shown by 16S rRNA gene analysis performed at the end of the incubation. At initial pH values of 3 and 4, sulfate reduction and cell growth occurred only after an extended lag phase, however, at a higher rate than in the less acidic assays. At the end of the growth phase, enrichments were dominated by Thermodesulfobium spp. suggesting that these sulfate reducers were better adapted to acidic conditions. Iron sulfides in the bulk phase were common in all assays, but specific aluminum precipitates formed in close association with cell surfaces and may function as a detoxification mechanism of dissolved Al species at low pH.

  5. Hollow-fiber liquid phase microextraction for lignin pyrolysis acids in aerosol samples and gas chromatography-mass spectrometry analysis.

    Science.gov (United States)

    Hyder, Murtaza; Jönsson, Jan Åke

    2012-08-03

    A method based on three-phase hollow fiber liquid phase microextraction was developed and successfully applied to aerosols for the analysis of lignin pyrolysis acids such as syringic acid, vanillic acid and p-salicylic acid. Important parameters related to extraction process like organic solvent for membrane phase, tri-n-octylphosphine (TOPO) oxide contents in organic solvent, stirring speed, extraction time etc. were optimized. 6-Undecanone with 15% TOPO contents (w/v) was found a suitable solvent for organic liquid membrane, 900 rpm was the optimum stirring speed and time of 4h was found optimum extraction time. Donor phase pH was 1.3 while acceptor phase pH was adjusted to 9.5. The optimized extraction method was used for the extraction of real aerosol samples. Analytes were derivatized using BSTFA containing 1% trimethylsilyl chloride and gas chromatography mass spectrometry was used for analysis. Very low limits of detection in the range 0.2-1.0 ng L(-1) were found, corresponding to 10-50 pg m(-3) of analytes in aerosols. Extraction efficiency obtained ranged 60.3-71.7% and enrichment factors ranged 3015-3585 times. The optimized method was successfully applied to aerosol samples and all of the selected analytes were detected in the analyzed samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. The impact of geoengineering aerosols on stratospheric temperature and ozone

    Energy Technology Data Exchange (ETDEWEB)

    Heckendorn, P; Luo, B P; Rozanov, E; Schraner, M; Peter, T [Institute for Atmospheric and Climate Science, ETH Zurich, 8092 Zurich (Switzerland); Weisenstein, D [AER, Lexington, MA (United States); Fueglistaler, S [DAMTP, University of Cambridge (United Kingdom); Thomason, L W, E-mail: patricia.heckendorn@env.ethz.c [NASA Langley Research Center, Hampton, VA (United States)

    2009-10-15

    Anthropogenic greenhouse gas emissions are warming the global climate at an unprecedented rate. Significant emission reductions will be required soon to avoid a rapid temperature rise. As a potential interim measure to avoid extreme temperature increase, it has been suggested that Earth's albedo be increased by artificially enhancing stratospheric sulfate aerosols. We use a 3D chemistry climate model, fed by aerosol size distributions from a zonal mean aerosol model, to simulate continuous injection of 1-10 Mt/a into the lower tropical stratosphere. In contrast to the case for all previous work, the particles are predicted to grow to larger sizes than are observed after volcanic eruptions. The reason is the continuous supply of sulfuric acid and hence freshly formed small aerosol particles, which enhance the formation of large aerosol particles by coagulation and, to a lesser extent, by condensation. Owing to their large size, these particles have a reduced albedo. Furthermore, their sedimentation results in a non-linear relationship between stratospheric aerosol burden and annual injection, leading to a reduction of the targeted cooling. More importantly, the sedimenting particles heat the tropical cold point tropopause and, hence, the stratospheric entry mixing ratio of H{sub 2}O increases. Therefore, geoengineering by means of sulfate aerosols is predicted to accelerate the hydroxyl catalyzed ozone destruction cycles and cause a significant depletion of the ozone layer even though future halogen concentrations will be significantly reduced.

  7. The Impact of Geoengineering Aerosols on Stratospheric Temperature and Ozone

    Science.gov (United States)

    Heckendorn, P.; Weisenstein, D.; Fueglistaler, S.; Luo, B. P.; Rozanov, E.; Schraner, M.; Thomason, L. W.; Peter, T.

    2011-01-01

    Anthropogenic greenhouse gas emissions are warming the global climate at an unprecedented rate. Significant emission reductions will be required soon to avoid a rapid temperature rise. As a potential interim measure to avoid extreme temperature increase, it has been suggested that Earth's albedo be increased by artificially enhancing stratospheric sulfate aerosols. We use a 3D chemistry climate model, fed by aerosol size distributions from a zonal mean aerosol model. to simulate continuous injection of 1-10 Mt/a into the lower tropical stratosphere. In contrast to the case for all previous work, the particles are predicted to grow to larger sizes than are observed after volcanic eruptions. The reason is the continuous supply of sulfuric acid and hence freshly formed small aerosol particles, which enhance the formation of large aerosol particles by coagulation and, to a lesser extent, by condensation. Owing to their large size, these particles have a reduced albedo. Furthermore, their sedimentation results in a non-linear relationship between stratospheric aerosol burden and annual injection, leading to a reduction of the targeted cooling. More importantly, the sedimenting particles heat the tropical cold point tropopause and, hence, the stratospheric entry mixing ratio of H2O increases. Therefore, geoengineering by means of sulfate aerosols is predicted to accelerate the hydroxyl catalyzed ozone destruction cycles and cause a significant depletion of the ozone layer even though future halogen concentrations will he significantly reduced.

  8. Formation of a Phyllosilicate-, K-feldspar-, and Sulfate-Bearing Hematite Ridge on Mauna Kea Volcano, Hawaii, Under Hydrothermal, Acid-Sulfate Conditions: Process and Mineralogical Analog for the Hematite Ridge on Mt. Sharp, Gale Crater, Mars.

    Science.gov (United States)

    Ming, D. W.; Morris, R. V.; Adams, M. E.; Catalano, J. G.; Graff, T. G.; Arvidson, R. E.; Guinness, E. A.; Hamilton, J. C.; Mertzman, S. A.; Fraeman, A.

    2015-12-01

    The Mars Science Laboratory rover Curiosity is currently moving upslope on Mt. Sharp in Gale Crater toward a hematite-bearing ridge. This hematite exposure was originally detected in CRISM spectra and subsequently mapped as part of a ~200 m wide, 6.5 km long ridge extending roughly parallel to the base of Mt. Sharp. CRISM spectra in the region suggest that hematite, smectite, and hydrated sulfates occur as secondary phases in lower layers of Mt. Sharp, separated by an unconformity from overlying anhydrous strata. A potential process and mineralogical analog is a hematite-bearing and weathering-resistant stratum (ridge) is exposed on the Puu Poliahu cinder cone on Mauna Kea (MK) volcano, Hawaii. The MK ridge is the product of hydrothermal alteration of basaltic precursors under acid-sulfate conditions. We are acquiring chemical and mineralogical (VNIR, Mid-IR, and backscatter Moessbauer spectroscopy, and transmission XRD) data on the MK ridge area that correspond to rover and orbiting spacecraft measurements at Gale Crater and elsewhere. The hematite-bearing stratum does not have detectable sulfate minerals by XRD, and hematite is variably present as up to mm-sized black crystals which, together with associated trioctahedral smectite and K-feldspar (from XRD), imply hydrothermal conditions. Adjacent to the MK hematite-bearing stratum are sulfates (jarosite and alunite) that are evidence for aqueous alteration under acid-sulfate conditions, and more soluble sulfates are absent but such phases would not persist if formed because of annual precipitation. Dioctahedral smectite is associated with red hematite and alunite-rich samples. The black and red hematite zones have the highest and lowest MgO/Al2O3 and K2O/Na2O ratios, respectively. Hematite, smectite, jarosite, and K-feldspar have been detected by Curiosity XRD downslope from the Mt. Sharp hematite ridge. MK field work and samples were obtained with PISCES partnership and OMKM, MKMB, BLNR, and KKMC permissions.

  9. Measurements of the HO2 uptake coefficients onto single component organic aerosols.

    Science.gov (United States)

    Lakey, P S J; George, I J; Whalley, L K; Baeza-Romero, M T; Heard, D E

    2015-04-21

    Measurements of HO2 uptake coefficients (γ) were made onto a variety of organic aerosols derived from glutaric acid, glyoxal, malonic acid, stearic acid, oleic acid, squalene, monoethanol amine sulfate, monomethyl amine sulfate, and two sources of humic acid, for an initial HO2 concentration of 1 × 10(9) molecules cm(-3), room temperature and at atmospheric pressure. Values in the range of γ < 0.004 to γ = 0.008 ± 0.004 were measured for all of the aerosols apart from the aerosols from the two sources of humic acid. For humic acid aerosols, uptake coefficients in the range of γ = 0.007 ± 0.002 to γ = 0.09 ± 0.03 were measured. Elevated concentrations of copper (16 ± 1 and 380 ± 20 ppb) and iron (600 ± 30 and 51 000 ± 3000 ppb) ions were measured in the humic acid atomizer solutions compared to the other organics that can explain the higher uptake values measured. A strong dependence upon relative humidity was also observed for uptake onto humic acid, with larger uptake coefficients seen at higher humidities. Possible hypotheses for the humidity dependence include the changing liquid water content of the aerosol, a change in the mass accommodation coefficient or in the Henry's law constant.

  10. The 2005 catastrophic acid crater lake drainage, lahar, and acidic aerosol formation at Mount Chiginagak volcano, Alaska, USA: Field observations and preliminary water and vegetation chemistry results

    Science.gov (United States)

    Schaefer, J.R.; Scott, W.E.; Evans, William C.; Jorgenson, J.; McGimsey, R.G.; Wang, B.

    2008-01-01

    A mass of snow and ice 400-m-wide and 105-m-thick began melting in the summit crater of Mount Chiginagak volcano sometime between November 2004 and early May 2005, presumably owing to increased heat flux from the hydrothermal system, or possibly from magma intrusion and degassing. In early May 2005, an estimated 3.8??106 m3 of sulfurous, clay-rich debris and acidic water, with an accompanying acidic aerosol component, exited the crater through a tunnel at the base of a glacier that breaches the south crater rim. Over 27 km downstream, the acidic waters of the flood inundated an important salmon spawning drainage, acidifying Mother Goose Lake from surface to depth (approximately 0.5 km3 in volume at a pH of 2.9 to 3.1), killing all aquatic life, and preventing the annual salmon run. Over 2 months later, crater lake water sampled 8 km downstream of the outlet after considerable dilution from glacial meltwater was a weak sulfuric acid solution (pH = 3.2, SO4 = 504 mg/L, Cl = 53.6 mg/L, and F = 7.92 mg/L). The acid flood waters caused severe vegetation damage, including plant death and leaf kill along the flood path. The crater lake drainage was accompanied by an ambioructic flow of acidic aerosols that followed the flood path, contributing to defoliation and necrotic leaf damage to vegetation in a 29 km2 area along and above affected streams, in areas to heights of over 150 m above stream level. Moss species killed in the event contained high levels of sulfur, indicating extremely elevated atmospheric sulfurcontent. The most abundant airborne phytotoxic constituent was likely sulfuric acid aerosols that were generated during the catastrophic partial crater lake drainage event. Two mechanisms of acidic aerosol formation are proposed: (1) generation of aerosol mist through turbulent flow of acidic water and (2) catastrophic gas exsolution. This previously undocumented phenomenon of simultaneous vegetationdamaging acidic aerosols accompanying drainage of an acidic crater

  11. Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Adele M.; Xue, Youjia [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Kinsela, Andrew S. [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Wilcken, Klaus M. [Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Collins, Richard N., E-mail: richard.collins@unsw.edu.au [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia)

    2016-03-15

    Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values < 3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with {sup 55}Fe and {sup 26}Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (> 70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO{sub 4}){sub 2}{sup −} and/or Me–NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. - Highlights: • CLASS discharge large amounts of metals and their speciation is poorly

  12. A multi-faceted approach to characterize acid-sulfate alteration processes in volcanic hydrothermal systems on Earth and Mars

    Science.gov (United States)

    Marcucci, Emma Cordts

    Acid-sulfate alteration is a dominant weathering process in high temperature, low pH, sulfur-rich volcanic environments. Additionally, hydrothermal environments have been proposed as locations where life could have originated on Earth. Based on the extensive evidence of flowing surface water and persistent volcanism, similar locations and processes could have existed on early Mars. Globally observed alteration mineral assemblages likely represent relic Martian hydrothermal settings. Yet the limited understanding of environmental controls, limits the confidence of interpreting the paleoconditions of these hydrothermal systems and assessing their habitability to support microbial life. This thesis presents a series of laboratory experiments, geochemical models, analog fieldwork, and Martian remote sensing to characterize distinguishing features and controls of acid-sulfate alteration. The experiments and models were designed to replicate alteration is a highly acidic, sulfurous, and hot field sites. The basaltic minerals were individually reacted in both experimental and model simulations with varying initial parameters to infer the geochemical pathways of acid-sulfate alteration on Earth and Mars. It was found that for a specific starting material, secondary mineralogies were consistent. Variations in pH, temperature and duration affected the abundance, shape, and size of mineral products. Additionally evaporation played a key role in secondary deposits; therefore, both alteration and evaporitic processes need to be taken into consideration. Analog volcanic sites in Nicaragua were used to supplement this work and highlight differences between natural and simulated alteration. In situ visible near-infrared spectroscopy demonstrated that primary lithology and gas chemistry were dominant controls of alteration, with secondary effects from environmental controls, such as temperature and pH. The spectroscopic research from the field was directly related to Mars

  13. Characterization of aerosol composition, concentrations, and sources at Baengnyeong Island, Korea using an aerosol mass spectrometer

    Science.gov (United States)

    Lee, Taehyoung; Choi, Jinsoo; Lee, Gangwoong; Ahn, Junyoung; Park, Jin Soo; Atwood, Samuel A.; Schurman, Misha; Choi, Yongjoo; Chung, Yoomi; Collett, Jeffrey L.

    2015-11-01

    To improve understanding of the sources and chemical properties of particulate pollutants on the western side of the Korean Peninsula, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) measured non-refractory fine (PM1) particles from May to November, 2011 at Baengnyeong Island, South Korea. Organic matter and sulfate were generally the most abundant species and exhibited maximum concentrations of 36 μg/m3 and 39 μg/m3, respectively. Nitrate concentrations peaked at 32 μg/m3 but were typically much lower than sulfate and organic matter concentrations. May, September, October, and November featured the highest monthly average concentrations, with lower concentrations typically observed from June through August. Potential source contribution function (PSCF) analysis and individual case studies revealed that transport from eastern China, an area with high SO2 emissions, was associated with high particulate sulfate concentrations at the measurement site. Observed sulfate aerosol sometimes was fully neutralized by ammonium but often was acidic; the average ammonium to sulfate molar ratio was 1.49. Measured species size distributions revealed a range of sulfate particle size distributions with modes between 100 and 600 nm. Organic aerosol source regions were widespread, including contributions from eastern China and South Korea. Positive matrix factorization (PMF) analysis indicated three "factors," or types of organic aerosol, comprising one primary, hydrocarbon-like organic aerosol (HOA) and two oxidized organic aerosol (OOA) components, including a more oxidized (MO-OOA) and a less oxidized (LO-OOA) oxidized organic aerosol. On average, HOA and OOA contributed 21% and 79% of the organic mass (OM), respectively, with the MO-OOA fraction nearly three times as abundant as the LO-OOA fraction. Biomass burning contributions to observed OM were low during the late spring/early summer agricultural burning season in eastern China, since

  14. Adsorptive removal of sulfate from acid mine drainage by polypyrrole modified activated carbons: Effects of polypyrrole deposition protocols and activated carbon source.

    Science.gov (United States)

    Hong, Siqi; Cannon, Fred S; Hou, Pin; Byrne, Tim; Nieto-Delgado, Cesar

    2017-10-01

    Polypyrrole modified activated carbon was used to remove sulfate from acid mine drainage water. The polypyrrole modified activated carbon created positively charged functionality that offered elevated sorption capacity for sulfate. The effects of the activated carbon type, approach of polymerization, preparation temperature, solvent, and concentration of oxidant solution over the sulfate adsorption capacity were studied at an array of initial sulfate concentrations. A hardwood based activated carbon was the more favorable activated carbon template, and this offered better sulfate removal than when using bituminous based activated carbon or oak wood activated carbon as the template. The hardwood-based activated carbon modified with polypyrrole removed 44.7 mg/g sulfate, and this was five times higher than for the pristine hardwood-based activated carbon. Various protocols for depositing the polypyrrole onto the activated carbon were investigated. When ferric chloride was used as an oxidant, the deposition protocol that achieved the most N(+) atomic percent (3.35%) while also maintaining the least oxygen atomic percent (6.22%) offered the most favorable sulfate removal. For the rapid small scale column tests, when processing the AMD water, hardwood-based activated carbon modified with poly pyrrole exhibited 33 bed volume compared to the 5 bed volume of pristine activated carbons. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Highly acidic glycans from sea cucumbers. Isolation and fractionation of fucose-rich sulfated polysaccharides from the body wall of Ludwigothurea grisea.

    Science.gov (United States)

    Mourão, P A; Bastos, I G

    1987-08-03

    The body wall of the sea cucumber contains high amounts of sulfated glycans, which differ in structure from glycosaminoglycans of animal tissues and also from the fucose-rich sulfated polysaccharides isolated from marine algae and from the jelly coat of sea urchin eggs. In Ludwigothurea grisea, glycans can be separated into three fractions which differ in molecular mass and chemical composition. The fraction containing a high-molecular-mass component has a high proportion of fucose and small amounts of amino sugars, whereas another fraction contains primarily a sulfated fucan. The third fraction, which represents the major portion of the sea cucumber polysaccharides, contains besides fucose, approximately equimolar proportions of glucuronic acid and amino sugars, and has a sulfate content higher than that in the other two fractions. Both D and L-isomers of fucose are found in these polysaccharides, and the sulfate is linked to the O-3 position of the fucose residues. The attachment position of the sulfate groups to the glucuronic acid units and amino sugars is still undetermined. It is possible that these compounds are involved in maintaining the integrity of the sea cucumber's body wall, in analogy with the role of other macromolecules in the vertebrate connective tissue.

  16. Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

    Science.gov (United States)

    Graff, Trevor G.; Morris, R. V.; Archilles C. N.; Agresti, D. G.; Ming, D. W.; Hamilton, J. C.; Mertzman, S. A.; Smith, J.

    2012-01-01

    Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.

  17. Effect of nitrate and sulfate relative abundance in PM2.5 on liquid water content explored through half-hourly observations of inorganic soluble aerosols at a polluted receptor site

    Science.gov (United States)

    Xue, Jian; Griffith, Stephen M.; Yu, Xin; Lau, Alexis K. H.; Yu, Jian Zhen

    2014-12-01

    Liquid water content (LWC) is the amount of liquid water on aerosols. It contributes to visibility degradation, provides a surface for gas condensation, and acts as a medium for heterogeneous gas/particle reactions. In this study, 520 half-hourly measurements of ionic chemical composition in PM2.5 at a receptor site in Hong Kong are used to investigate the dependence of LWC on ionic chemical composition, particularly on the relative abundance of sulfate and nitrate. LWC was estimated using a thermodynamic model (AIM-III). Within this data set of PM2.5 ionic compositions, LWC was highly correlated with the multivariate combination of sulfate and nitrate concentrations and RH (R2 = 0.90). The empirical linear regression result indicates that LWC is more sensitive to nitrate mass than sulfate. During a nitrate episode, the highest LWC (80.6 ± 17.9 μg m-3) was observed and the level was 70% higher than that during a sulfate episode despite a similar ionic PM2.5 mass concentration. A series of sensitivity tests were conducted to study LWC change as a function of the relative nitrate and sulfate abundance, the trend of which is expected to shift to more nitrate in China as a result of SO2 reduction and increase in NOx emission. Starting from a base case that uses the average of measured PM2.5 ionic chemical composition (63% SO42-, 11% NO3-, 19% NH4+, and 7% other ions) and an ionic equivalence ratio, [NH4+]/(2[SO42-] + [NO3-]), set constant to 0.72, the results show LWC would increase by 204% at RH = 40% when 50% of the SO42- is replaced by NO3- mass concentration. This is largely due to inhibition of (NH4)3H(SO4)2 crystallization while PM2.5 ionic species persist in the aqueous phase. At RH = 90%, LWC would increase by 12% when 50% of the SO42- is replaced by NO3- mass concentration. The results of this study highlight the important implications to aerosol chemistry and visibility degradation associated with LWC as a result of a shift in PM2.5 ionic chemical

  18. Influence of Biomass Burning on Temporal and Diurnal Variations of Acidic Gases, Particulate Nitrate, and Sulfate in a Tropical Urban Atmosphere

    OpenAIRE

    Sailesh N. Behera; Rajasekhar Balasubramanian

    2014-01-01

    The present study investigated the temporal and diurnal distributions of atmospheric acidic gases (sulphur dioxide (SO2), nitrous acid (HONO), and nitric acid (HNO3)) and those of particulate nitrate (NO3-) and sulfate (SO42-) through a comprehensive field campaign during the largest smoke haze episode in Singapore, a representative country in Southeast Asia (SEA). To identify the atmospheric behavior of these pollutants during the smoke haze period, the data generated from the measurement ca...

  19. The ceric sulfate dosimeter

    DEFF Research Database (Denmark)

    Bjergbakke, Erling

    1970-01-01

    The process employed for the determination of absorbed dose is the reduction of ceric ions to cerous ions in a solution of ceric sulfate and cerous sulfate in 0.8N sulfuric acid: Ce4+→Ce 3+ The absorbed dose is derived from the difference in ceric ion concentration before and after irradiation...

  20. Selectively leaching Cu(Ⅱ) and Ni(Ⅱ) from acid mine drainage sludge by using ethylenediamine-ammonium sulfate

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A method based on controlling the complexation-precipitation equilibrium of metal ions was proposed to selectively recover nickel and copper from hydroxide sludge formed by lime neutralization of acid mine drainage(AMD). Ethylenediamine(EDA) and ammonium sulfate were chosen as complex reagent and precipitating reagent, respectively, to dissolve target metal hydroxides from sludge and limit useless metal ions in the pregnant solution. Results from both synthetic and natural samples show the excellent selectivity for the target metals(copper and nickel) against Fe(Ⅲ), Ca(Ⅱ) and Mg(Ⅱ), 99% recovery of Cu(Ⅱ) and Ni(Ⅱ) and shorter leaching time can be reached by this process, and the resultant solution can be used for direct electrowinning. The optimum operating conditions are: pH=9~11, ρ(EDA)=40g/L, ammonium sulfate 50g/L, leaching time 5h(for natural sample) and 2.5h(for synthetic sludge), liquid to solid ratio being 4 with mechanical stirring at room temperature.

  1. Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

    Science.gov (United States)

    Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

    2016-03-15

    Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported.

  2. Chloride, gluconate, sulfate, and short-chain fatty acids affect calcium flux rates across the sheep forestomach epithelium.

    Science.gov (United States)

    Leonhard-Marek, S; Becker, G; Breves, G; Schröder, B

    2007-03-01

    In ruminants, more than 50% of overall gastrointestinal Ca absorption can occur preintestinally, and the anions of orally applied Ca salts are thought to play an important role in stimulating ruminal Ca absorption. This assumption is based mainly on ion-exchange studies that have used gluconate as the control anion, which may bind Ca2+ ions and interfere with treatment effects. In the present study, we investigated the distinct effects of different anions on Ca absorption across the sheep rumen and on the concentration of free Ca2+ ions ([Ca2+]ion). We showed that gluconate, sulfate, and short-chain fatty acids (SCFA) remarkably reduced [Ca2+]ion in buffer solutions. Nevertheless, increasing the Cl or SCFA concentration by 60 mM stimulated net ruminal Ca absorption 5- to 7-fold, but these effects could be antagonized by gluconate. Therefore, ion-exchange experiments must be (re)evaluated very carefully, because changes in [Ca2+]ion in the presence of gluconate, sulfate, or SCFA not only might entail an underestimation of Ca flux rates, but also might have effects on other cellular pathways that are Ca2+ dependent. Concerning the optimal Ca supply for dairy cows, the present study suggests that CaCl2 formulations and Ca salts of the SCFA stimulate Ca absorption across the rumen wall and are beneficial in preventing or correcting a Ca deficiency.

  3. On the composition of ammonia-sulfuric-acid ion clusters during aerosol particle formation

    Science.gov (United States)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, in close resemblance to the acid-base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid-base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that electrically neutral NH3-H2SO4 clusters, unobservable in this study, have generally the same composition as ionic clusters for [NH3] / [H2SO4] > 10. We expect that NH3-H2SO4 clusters form and grow also mostly by Δm/Δn > 1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3-H2SO4 anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH3-H2SO4 clusters in boundary layer particle formation remains to be resolved.

  4. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    Science.gov (United States)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2014-05-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm / Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, in close resemblance to the acid-base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid-base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that yet unobservable electrically neutral NH3-H2SO4 clusters grow by generally the same mechanism as ionic clusters, particularly for [NH3] / [H2SO4]>10. We expect that NH3-H2SO4 clusters form and grow also mostly by Δm / Δn>1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3-H2SO4 anion clusters during new particle formation in the Finnish boreal forest. However, the exact role of NH3-H2SO4 clusters in boundary layer particle formation remains to be resolved.

  5. Infrared spectroscopic studies of the heterogeneous reaction of ozone with dry maleic and fumaric acid aerosol particles.

    Science.gov (United States)

    Nájera, Juan J; Percival, Carl J; Horn, Andrew B

    2009-10-28

    Dicarboxylic acids, either directly emitted or formed in chemical processes, are found to be a significant component of tropospheric aerosols. To assess any potential chemical transformation of short unsaturated dicarboxylic acids in tropospheric heterogeneous chemistry, maleic and fumaric acid were selected as surrogates in this study. A novel aerosol flow tube apparatus is employed to perform kinetic studies of the oxidation of these organic compounds by gas-phase ozone. The system consists of a particle generation system, a vertically oriented glass flow tube and an infrared observation White cell with a Fourier transform infrared (FTIR) spectrometer for the detection system. A flow of single component organic aerosols with mean diameters ranging between 0.7 and 1.1 microm is introduced in a flow tube, in which the particles are subsequently exposed to a known concentration of ozone for a controlled period of time. A band assignment of infrared vibrational frequencies for dry maleic and fumaric acid aerosol spectra is presented. These studies are complemented with off-line analysis on the reaction products. The reaction exhibited pseudo-first-order kinetics on gas product formation, and the pseudo-first-order rate coefficients displayed a Langmuir-Hinshelwood dependence on gas-phase ozone concentration for both materials. By assuming a Langmuir-Hinshelwood behaviour, the following parameters were obtained: for the reaction of maleic acid aerosols, K(O3) = (3.3 + 0.5) x 10(-16) cm3 molecule(-1) and k(I)(max) = (0.038 + 0.004) s(-1); for the reaction of fumaric acid aerosols, K(O3) = (1.6 + 0.5) x 10(-16) cm3 molecule(-1) and k(I)(max) = (0.048 + 0.007) s(-1), where K(O3) is a parameter that describes the partitioning of ozone to the particle surface and k is the maximum pseudo-first-order coefficient at high ozone concentrations. Apparent reactive uptake coefficients were estimated from the pseudo-first-order rate coefficient and a trend of decreasing uptake

  6. [Effectiveness of iron amino acid chelate versus ferrous sulfate as part of a food complement in preschool children with iron deficiency, Medellín, 2011].

    Science.gov (United States)

    Rojas, Maylen Liseth; Sánchez, Juliana; Villada, Óscar; Montoya, Liliana; Díaz, Alejandro; Vargas, Cristian; Chica, Javier; Herrera, Ana Milena

    2013-01-01

    Iron depleted deposits are the first link in the chain of events leading to iron deficiency which is the most prevalent nutritional shortage and main cause of anemia worldwide. This situation can be prevented through food fortification. To compare the efficacy of amino acid chelate iron with ferrous sulfate as fortifier of a dietary complement in preschoolers with iron deficiency. This study was a blinded clinical trial with randomized groups. We analyzed 56 preschoolers with iron deficiency (ferritin ferrous sulfate form. After two months, hemoglobin, hematocrit and serum ferritin concentrations were measured. In the ferrous sulfate group, ferritin concentration increased from 18.8 ng/ml to 24.1 ng/ml, while the variation was of 18.4 ng/ml to 29.7 ng/ml in the amino acid chelate group, with statistically differences in both cases. Serum ferritin was different between groups, being higher in iron amino acid chelate group (p=0.022). Hemoglobin and hematocrit levels did not change after the intervention. Adverse reactions in the ferrous sulfate group were 35.7%, compared with 42.9% in the iron amino acid chelate group; 5 children had respiratory tract infection, without statistical differences. Both compounds increased serum ferritin concentration, with a higher increase in those who were given milk with iron amino acid chelate. There were no differences in the adverse reactions and infections incidences between the groups.

  7. Enhancement of bacterial iron and sulfate respiration for in situ bioremediation of acid mine drainage sites: a case study

    Energy Technology Data Exchange (ETDEWEB)

    Bilgin, A.A.; Harrington, J.M.; Silverstein, J. [ARCADIS G& amp; M, Highlands Ranch, CO (United States)

    2007-08-15

    The prevention of acid mine drainage (AMD) in situ is more attractive than down-gradient treatment alternatives that do not involve source control. AMD source control can be achieved by shifting the microbial activity in the sulfidic rock from pyrite oxidation to anaerobic heterotrophic activity. This is achieved by adding biodegradable organic carbon amendments to the sulfidic rock. This technique was applied to an abandoned coal mine pool in Pennsylvania. The pool had a pH of 3.0 to 3.5. Following treatment, near-neutral pH and decreased effluent heavy metal concentrations were achieved. In situ bioremediation by the enhancement of bacterial iron and sulfate reduction is a promising technology for AMD prevention.

  8. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

    Science.gov (United States)

    Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and (1)H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

  9. Water Activities and Osmotic Coefficients of Aqueous Solutions of Five Alkyl-Aminium Sulfates and Their Mixtures with H2SO4 at 25 oC

    OpenAIRE

    Sauerwein, Meike; Clegg, Simon

    2015-01-01

    Alkylaminium sulfates are frequently detected in ambient aerosols, and are believed to be important in the nucleation of new particles in the atmosphere, despite their comparatively low gas phase concentrations. In this study water activities and osmotic coefficients have been measured, using a chilled mirror dew point technique, of aqueous mixtures of sulfuric acid and the following alkylaminium sulfates: methylaminium, ethylaminium, dimethylaminium, diethylaminium and trimethylaminium sulfa...

  10. Inactivation of salmonella in biofilms and on chicken cages and preharvest poultry by levulinic Acid and sodium dodecyl sulfate.

    Science.gov (United States)

    Zhao, Tong; Zhao, Ping; Cannon, Jennifer L; Doyle, Michael P

    2011-12-01

    Surface contamination (skin and feathers) of broilers with Salmonella occurs primarily during growth and transportation. Immediately after transporting chickens, chicken cage doors were sprayed with a foam containing 3% levulinic acid plus 2% sodium dodecyl sulfate (SDS). Samples were collected for Salmonella assay after 45 min. Salmonella on cage doors was reduced from 19% (19 of 100 doors) before treatment to 1% (1 of 100 doors) after treatment, coliform counts were reduced from 6 to 8 to 2 to 4 log CFU/9 cm(2), and aerobic plate counts were reduced from 7 to 9 to 4 to 6 log CFU/9 cm(2). Whole chicken carcasses with feathers were inoculated with 10(8) CFU of Salmonella Enteritidis, soaked for 5 min at 21°C in 72 liters of a treatment or control solution, and assayed for Salmonella. Salmonella counts on chickens treated with water were 6.8 to 8.5 log CFU/9 cm(2), those treated with 50 ppm of calcium hypochlorite were 7.6 to 8.9 log CFU/9 cm(2), and those treated with 3% levulinic acid plus 2% SDS were 4-log reduction). Results of biofilm studies on surfaces of various materials revealed that a 3% levulinic acid plus 2% SDS treatment used as either a foam or liquid for 10 min effectively reduced Salmonella populations by 5 and >6 log CFU/cm(2), respectively.

  11. Water-soluble Organic Components in Aerosols Associated with Savanna Fires in Southern Africa: Identification, Evolution and Distribution

    Science.gov (United States)

    Gao, Song; Hegg, Dean A.; Hobbs, Peter V.; Kirchstetter, Thomas W.; Magi, Brian I.; Sadilek, Martin

    2003-01-01

    During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze and smoke aerosols, respectively. For the smoke aerosols, levoglucosan was the most abundant carbohydrate species, while gluconic acid was tentatively identified as the most abundant organic acid. The mass abundance and possible source of each class of identified species are discussed, along with their possible formation pathways. The combustion phase of a fire had an impact on the chemical composition of the emitted aerosols. Secondary formation of sulfate, nitrate, levoglucosan, and several organic acids occurred during the initial aging of smoke aerosols. It is likely that under certain conditions, some carbohydrate species in smoke aerosols, such as levoglucosan, were converted to organic acids during upward transport.

  12. Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols: implications for photochemical production and degradation in smoke layers

    Directory of Open Access Journals (Sweden)

    S. Kundu

    2009-09-01

    Full Text Available Aerosols in the size class <2.5 μm (6 daytime and 9 nighttime samples were collected at a pasture site in Rondônia, Brazil, during the intensive biomass burning period of 16–26 September 2002 as part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC. Homologous series of dicarboxylic acids (C2–C11 and related compounds (ketocarboxylic acids and dicarbonyls were identified using gas chromatography and GC/mass spectrometry (GC/MS. Among the species detected, oxalic acid was found to be the most abundant, followed by succinic, malonic and glyoxylic acids. Average concentrations of total dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the aerosol samples were 2180, 167 and 56 ng m−3, respectively. These are 2–8, 3–11 and 2–16 times higher, respectively, than those reported in urban aerosols, such as in 14 Chinese megacities. Higher ratios of dicarboxylic acids and related compounds to biomass burning tracers (levoglucosan and K+ were found in the daytime than in the nighttime, suggesting an importance of photochemical production. On the other hand, higher ratios of oxalic acid to other dicarboxylic acids and related compounds normalized to biomass burning tracers (levoglucosan and K+ in the daytime provide evidence for the possible degradation of dicarboxylic acids (≥C3 in this smoke-polluted environment. Assuming that these and related compounds are photochemically oxidized to oxalic acid in the daytime and given their linear relationship, they could account for, on average, 77% of the formation of oxalic acid. The remaining portion of oxalic acid may have been directly emitted from biomass burning as suggested by a good correlation with the biomass burning tracers (K+, CO and ECa and organic carbon (OC. However, photochemical production from other precursors

  13. Isotopic mass independent signature of black crusts: a proxy for atmospheric aerosols formation in the Paris area (France).

    Science.gov (United States)

    Genot, Isabelle; Martin, Erwan; Yang, David Au; De Rafelis, Marc; Cartigny, Pierre; Wing, Boswell; Le Gendre, Erwann; Bekki, Slimane

    2016-04-01

    In view of the negative forcing of the sulfate aerosols on climate, a more accurate understanding of the formation of these particles is crucial. Indeed, despite the knowledge of their effects, uncertainties remain regarding the formation of sulfate aerosols, particularly the oxidation processes of S-bearing gases. Since the discovery of oxygen and sulfur mass independent fractionation (O- and S-MIF) processes on Earth, the sulfate isotopic composition became essential to investigate the atmospheric composition evolution and its consequences on the climate and the biosphere. Large amount of S-bearing compounds (SO2 mainly) is released into the atmosphere by anthropogenic and natural sources. Their oxidation in the atmosphere generates sulfate aerosols, H2SO4, which precipitate on the earth surface mainly as acid rain. One consequence of this precipitation is the formation of black crust on buildings made of carbonate stones. Indeed the chemical alteration of CaCO3 by H2SO4 leads to gypsum (CaSO4·2H2O) concretions on building walls. Associated to other particles, gypsum forms black-crusts. Therefore, black crusts acts as 'sulfate aerosol traps', meaning that their isotopic composition reveals the composition and thus the source and formation processes of sulfate aerosols in the atmosphere in a specific region. In this study we collected 37 black crusts on a 300km NW-SE profile centered on Paris (France). In our samples, sulfate represent 40wt.% and other particles 60wt.% of the black crusts. After sulfate extraction from each samples we measured their O- and S-isotopes composition. Variations of about 10‰ in δ18O and δ34S are observed and both O-MIF (Δ17O from 0 to 1.4‰) and S-MIF (Δ33S from 0 to -0.3‰) compositions have been measured. In regards to these compositions we can discuss the source and formation (oxidation pathways) of the sulfate aerosols in troposphere above the Paris region that covers urban, rural and coastal environments. Furthermore

  14. A global off-line model of size-resolved aerosol microphysics: II. Identification of key uncertainties

    Directory of Open Access Journals (Sweden)

    D. V. Spracklen

    2005-01-01

    reasonable uncertainty ranges; (5 sulfate and sea salt derived CCN concentrations are particularly sensitive to primary particle emissions, with global mean MBL sulfate and sea salt CCN changing by up to 27% and local concentrations over continental regions changing by more than 100% when the percentage of anthropogenic SO2 emitted as particulates is changed from 0 to 5%; (6 large changes in sea spray flux have insignificant effects on global sulfate aerosol except when the mass accommodation coefficient of sulfuric acid on the salt particles is set unrealistically low.

  15. Abiotic oxidation of pyrite by Fe(III) in acidic media and its implications for sulfur isotope measurements of lattice-bound sulfate in sediments

    Digital Repository Service at National Institute of Oceanography (India)

    Mazumdar, A.; Goldberg, T.; Strauss, H

    from our pure pyrite oxidation experiments show that in a solution of acidic pH, the amount of sulfate formed is very similar under both oxygenated and oxygen-free experimental conditions which is suggestive of the dominant role of Fe sup(3+) in pyrite...

  16. 1-Butyl-3-methylimidazolium Hydrogen Sulfate [bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Formylation of Alcohols

    Institute of Scientific and Technical Information of China (English)

    NIKNAM Khodabakhsh; ZOLFIGOL Mohammad Ali; SABERI Dariush; KHONBAZI Mahdi

    2009-01-01

    1-Butyl-3-methylimidazolium hydrogen sulfate [bmim]HSO4 as an acidic ionic liquid was prepared and used as a catalyst for the formylation of alcohols with ethyl formate at room temperature with good to excellent yields.A good selectivity was observed for the formylation of primary alcohols in the presence of tertiary alcohols.

  17. The Oxidation of Fe(II) in Acidic Sulfate Solutions with Air at Elevated Pressures. Part 1. Kinetics above 1 M H2SO4

    NARCIS (Netherlands)

    Wermink, Wouter N.; Versteeg, Geert F.

    2017-01-01

    The oxidation of ferrous ions in acidic sulfate solutions at elevated air pressures was investigated. The effect of the Fe2+ concentration, initial H2SO4 concentration and partial oxygen pressure on the reaction rate were determined at three different temperatures, that is, T = 90, 70, and 50

  18. Genome-Wide Expression Analysis of Human In Vivo Irritated Epidermis: Differential Profiles Induced by Sodium Lauryl Sulfate and Nonanoic Acid

    DEFF Research Database (Denmark)

    Clemmensen, Anders; Andersen, Klaus E; Clemmensen, Ole

    2010-01-01

    the differential molecular events induced in the epidermis by different irritants, we collected sequential biopsies ((1/2), 4, and 24 hours after a single exposure and at day 11 after repeated exposure) from human volunteers exposed to either sodium lauryl sulfate (SLS) or nonanoic acid (NON). Gene expression...

  19. Laboratory Hydrothermal Alteration of Basaltic Tephra by Acid Sulfate Solutions: An Analog Process for Martian Weathering

    Science.gov (United States)

    Golden, D. C.; Ming, D. W.; Morris, R. V.

    2003-01-01

    The objective of this study is to conduct simulated Mars-like weathering experiments in the laboratory to determine the weathering products that might form during oxidative, acidic weathering of Mars analog materials.

  20. Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006

    Directory of Open Access Journals (Sweden)

    C. Fountoukis

    2009-03-01

    Full Text Available Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. For particle sizes up to 1μm diameter, semi-volatile partitioning requires 15–30 min to equilibrate; longer time is typically required during the night and early morning hours. Aerosol and gas-phase speciation always exhibits substantial temporal variability, so that aerosol composition measurements (bulk or size-resolved obtained over large integration periods are not reflective of its true state. When the aerosol sulfate-to-nitrate molar ratio is less than unity, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations is required to accurately predict the partitioning and phase state of aerosols.

  1. Size distributions of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

    Directory of Open Access Journals (Sweden)

    K. Kawamura

    2012-09-01

    Full Text Available Atmospheric aerosol samples of PM2.5 and PM10 were collected during the wet and dry seasons in 2011 from a rural site in Tanzania and analysed for water-soluble dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids using a gas chromatography (GC and GC/mass spectrometry. Here we report the size distribution and sources of diacids and related compounds for wet and dry seasons. Oxalic acid (C2 was found as the most abundant diacid species followed by succinic and/or malonic acids whereas glyoxylic acid and glyoxal were the dominant ketoacids and α-dicarbonyls, respectively in both seasons in PM2.5 and PM10. Mean concentration of C2 in PM2.5 (121.5± 46.6 ng m−3 was lower in wet season than dry season (258.1± 69.5 ng m−3. Similarly, PM10 samples showed lower concentration of C2 (168.6 ± 42.4 ng m−3 in wet season than dry season (292.4± 164.8 ng m−3. Relative abundances of C2 in total diacids were 65.4% and 67.1% in PM2.5 and 64.6% and 63.9% in PM10 in the wet and dry seasons, respectively. Total concentrations of diacids (289–362 m−3, ketoacids (37.8–53.7ng m−3, and α-dicarbonyls (5.7–7.8 ng m−3 in Tanzania are higher to those reported at a rural background site in Nylsvley (South Africa but comparable or lower to those reported from sites in Asia and Europe. Diacids and ketoacids were found to be present mainly in the fine fraction in both seasons (total α-dicarbonyls in the dry season, suggesting a production of organic aerosols from pyrogenic sources and photochemical oxidations. The averaged contributions of total diacid carbon to aerosol total carbon were 1.4% in PM2.5 and 2.1% in PM10 in wet season and 3.3% in PM2.5 and 3.9% in PM10 in dry season whereas those to water-soluble organic carbon were 2.2% and 4.7% inPM2.5 and 3.1% and 5.8% in PM10 during the wet and dry seasons, respectively. These ratios suggest an enhanced photochemical oxidation of organic precursors and heterogeneous

  2. Sulfur mass loading of the atmosphere from volcanic eruptions: Calibration of the ice core record on basis of sulfate aerosol deposition in polar regions from the 1982 El Chichon eruption

    Science.gov (United States)

    Sigurdsson, Haraldur; Laj, Paolo

    1990-01-01

    Major volcanic eruptions disperse large quantities of sulfur compound throughout the Earth's atmosphere. The sulfuric acid aerosols resulting from such eruptions are scavenged by snow within the polar regions and appear in polar ice cores as elevated acidity layers. Glacio-chemical studies of ice cores can, thus, provide a record of past volcanism, as well as the means for understanding the fate of volcanic sulfur in the atmosphere. The primary objectives of this project are to study the chemistry and physical properties of volcanic fallout in a Greenland Ice Core in order to evaluate the impact of the volcanic gases on the atmospheric chemistry and the total atmospheric mass of volcanic aerosols emitted by major volcanic eruptions. We propose to compare the ice core record to other atmospheric records performed during the last 10 years to investigate transport and deposition of volcanic materials.

  3. Water-soluble dicarboxylic acids and ω-oxocarboxylic acids in size-segregated aerosols over northern Japan during spring: sources and formation processes

    Science.gov (United States)

    Deshmukh, Dhananjay Kumar; Kawamura, Kimitaka; Kobayashi, Minoru; Gowda, Divyavani

    2016-04-01

    Seven sets (AF01-AF07) of size-segregated aerosol (12-sizes) samples were collected using a Micro-Orifice Uniform Deposit Impactor (MOUDI) in Sapporo, Japan during the spring of 2001 to understand the sources and atmospheric processes of water-soluble organic aerosols in the outflow region of Asian dusts. The samples were analyzed for dicarboxylic acids (C2-C12) and ω-oxocarboxylic acids as well as inorganic ions. The molecular distribution of diacids showed the predominance of oxalic acid (C2) followed by malonic and succinic acids whereas ω-oxoacids showed the predominance of glyoxylic acid (ωC2) in size-segregated aerosols. SO42- and NH4+ are enriched in submicron mode whereas NO3- and Ca2+ are in supermicron mode. Most of diacids and ω-oxoacids are enriched in supermicron mode in the samples (AF01-AF03) influenced by the long-range transport of mineral dusts whereas enhanced presence in submicron mode was observed in other sample sets. The strong correlations of C2 with Ca2+ (r = 0.95-0.99) and NO3- (r = 0.96-0.98) in supermicron mode in the samples AF01-AF03 suggest the adsorption or production of C2 diacid via heterogeneous reaction on the surface of mineral dust during long-range atmospheric transport. The preferential enrichment of diacids and ω-oxoacids in mineral dust has important implications for the solubility and cloud nucleation properties of the dominant fraction of water-soluble organic aerosols. This study demonstrates that biofuel and biomass burning and mineral dust originated in East Asia are two major factors to control the size distribution of diacids and related compounds over northern Japan.

  4. A Pacific Aerosol Survey - Part 1: A Decade Of Data On Natural Particle Production, Evolution And Mixing In The Troposphere

    Science.gov (United States)

    Clarke, A. D.; Kapustin, V.

    2001-12-01

    Integration of extensive aerosol data collected during the past decade around the Pacific Basin provides a preliminary assessment of aerosol microphysics for this region and cycling of aerosol in the troposphere. These include aircraft based data collected as part of numerous field experiments supported by NASA, NSF and NOAA (GLOBE, ACE1, PEM-Tropics A&B). Vertical profiles of aerosol concentrations, size distributions and optical properties were used to characterize aerosol structure in the Pacific troposphere from 70S to 70N. The in-situ data is placed in the context of meteorological regimes over the Pacific as well as processes associated with particle formation, growth and evolution and include dust, pollution, sea-salt, sulfates and clean cloud-processed air. Above the ITCZ in the tropical free troposphere (FT) aerosol are characterized by low aerosol mass but very high number concentrations that appear to form from sulfuric acid (nucleation) in convective regions, near cloud edges and occasionally near edges of continental aerosol plumes. These age and subside to become effective CCN when mixed into the marine boundary layer where they continue to grow and help replenish MBL aerosol depleted through precipitation. Our data in the tropics suggest entrainment rates of about 0.5 cm s-1. The volatility of these ``new" aerosol allow them to be compared to the fewer number but larger aerosol more evident in the mid-latitude FT. The latter are often internally mixed and with a non-volatile core indicative of black carbon with volatile components (sulfate, organics etc.). Both constituents may dominate the scattering and absorption properties of the aerosol even though the increase in continentally derived aerosol generally dominate the mass. The FT in the subtropics tends to exhibit frequent and marked transitions and mixing between these clean and continental aerosol types.

  5. MSA in Beijing aerosol

    Institute of Scientific and Technical Information of China (English)

    YUAN Hui; WANG Ying; ZHUANG Guoshun

    2004-01-01

    Methane sulphonate (MSA) and sulfate (SO42-), the main oxidation products of dimethyl sulfide (DMS), are the target of atmospheric chemistry study, as sulfate aerosol would have important impact on the global climate change. It is widely believed that DMS is mainly emitted from phytoplankton production in marine boundary layer (MBL), and MSA is usually used as the tracer of non-sea-salt sulfate (nss- SO42-) in marine and coastal areas (MSA/SO42- = 1/18). Many observations of MSA were in marine and coastal aerosols. To our surprise, MSA was frequently (>60%) detected in Beijing TSP, PM10, and PM2.5 aerosols, even in the samples collected during the dust storm period. The concentrations of MSA were higher than those measured in marine aerosols. Factor analysis, correlation analysis and meteorology analysis indicated that there was no obvious marine influence on Beijing aerosols. DMS from terrestrial emissions and dimethyl sulphoxide (DMSO) from industrial wastes could be the two possible precursors of MSA. Warm and low-pressure air masses and long time radiation were beneficial to the formation of MSA. Anthropogenic pollution from regional and local sources might be the dominant contributor to MSA in Beijing aerosol. This was the first report of MSA in aerosols collected in an inland site in China. This new finding would lead to the further study on the balance of sulfur in inland cities and its global biogeochemical cycle.

  6. Broadband measurements of aerosol extinction in the ultraviolet spectral region

    Science.gov (United States)

    Washenfelder, R. A.; Flores, J. M.; Brock, C. A.; Brown, S. S.; Rudich, Y.

    2013-04-01

    Aerosols influence the Earth's radiative budget by scattering and absorbing incoming solar radiation. The optical properties of aerosols vary as a function of wavelength, but few measurements have reported the wavelength dependence of aerosol extinction cross sections and complex refractive indices. We describe a new laboratory instrument to measure aerosol optical extinction as a function of wavelength, using cavity enhanced spectroscopy with a broadband light source. The instrument consists of two broadband channels which span the 360-390 and 385-420 nm spectral regions using two light emitting diodes (LED) and a grating spectrometer with charge-coupled device (CCD) detector. We determined aerosol extinction cross sections and directly observed Mie scattering resonances for aerosols that are purely scattering (polystyrene latex spheres and ammonium sulfate), slightly absorbing (Suwannee River fulvic acid), and strongly absorbing (nigrosin dye). We describe an approach for retrieving refractive indices as a function of wavelength from the measured extinction cross sections over the 360-420 nm wavelength region. The retrieved refractive indices for PSL and ammonium sulfate agree within uncertainty with the literature values for this spectral region. The refractive index determined for nigrosin is 1.78 (± 0.03) + 0.19 (± 0.08)i at 360 nm and 1.63 (± 0.03) + 0.21 (± 0.05)i at 420 nm. The refractive index determined for Suwannee River fulvic acid is 1.71 (± 0.02) + 0.07 (± 0.06)i at 360 nm and 1.66 (± 0.02) + 0.06 (± 0.04)i at 420 nm. These laboratory results support the potential for a field instrument capable of determining ambient aerosol optical extinction, average aerosol extinction cross section, and complex refractive index as a function of wavelength.

  7. Non-sea-salt sulfate in the marine boundary layer and its possible impact on chloride depletion

    Institute of Scientific and Technical Information of China (English)

    XIE Zhouqing; SUN Liguang; Cole-Dai Jihong

    2005-01-01

    Aerosol samples were collected on board the research vessel Xuelong during the Fifteenth Chinese Antarctic Research Expedition (CHINARE XV) in November 1998-April 1999 and the First Chinese Arctic Research Expedition in July-September 1999.The areas traversed by the expeditionary cruises include the Arctic Ocean, the western North Pacific Ocean and the eastern Indian Ocean,covering 75°N-69°S and 75°E-133°W. Aerosol samples were also taken at the Chinese Zhongshan Station in East Antarctica during the CHINARE XV. Analysis of the samples yielded concentrations of non-sea-salt sulfate and other soluble chemical species in the marine boundary layer. The data suggest that the chemical composition of the marine aerosols is influenced by three major sources:continental air masses, primary oceanic emissions, and secondary marine aerosols originated from oceanic emissions. The results show that, awing to strong anthropogenic sulfur emissions from the Asian continent, non-sea-salt sulfate concentrations in the Northern Hemisphere (the western North Pacific) marine aerosol are significantly higher than those in the Southern Hemisphere (the eastern Indian Ocean). Aerosol non-sea-salt sulfate concentrations appear to be inversely correlated with aerosol non-sea-salt chloride which shows significantly negative values, indicating the loss of chloride by sea salts, in most aerosol samples. Since gaseous HCl may be involved in chemical reactions that deplete atmospheric ozone in the marine boundary layer (MBL), high levels of acidic non-sea-salt-sulfate released by human activities in the low and mid-latitudes of the Northern Hemisphere may become an important potential contributor to the loss of atmospheric ozone in the MBL.

  8. Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes

    Science.gov (United States)

    Riva, Matthieu; Da Silva Barbosa, Thais; Lin, Ying-Hsuan; Stone, Elizabeth A.; Gold, Avram; Surratt, Jason D.

    2016-09-01

    We report the formation of aliphatic organosulfates (OSs) in secondary organic aerosol (SOA) from the photooxidation of C10-C12 alkanes. The results complement those from our laboratories reporting the formation of OSs and sulfonates from gas-phase oxidation of polycyclic aromatic hydrocarbons (PAHs). Both studies strongly support the formation of OSs from the gas-phase oxidation of anthropogenic precursors, as hypothesized on the basis of recent field studies in which aromatic and aliphatic OSs were detected in fine aerosol collected from several major urban locations. In this study, dodecane, cyclodecane and decalin, considered to be important SOA precursors in urban areas, were photochemically oxidized in an outdoor smog chamber in the presence of either non-acidified or acidified ammonium sulfate seed aerosol. Effects of acidity and relative humidity on OS formation were examined. Aerosols collected from all experiments were characterized by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS). Most of the OSs identified could be explained by formation of gaseous epoxide precursors with subsequent acid-catalyzed reactive uptake onto sulfate aerosol and/or heterogeneous reactions of hydroperoxides. The OSs identified here were also observed and quantified in fine urban aerosol samples collected in Lahore, Pakistan, and Pasadena, CA, USA. Several OSs identified from the photooxidation of decalin and cyclodecane are isobars of known monoterpene organosulfates, and thus care must be taken in the analysis of alkane-derived organosulfates in urban aerosol.

  9. Inactivation of Salmonella spp. and Listeria spp. by Palmitic, Stearic, and Oleic Acid Sophorolipids and Thiamine Dilauryl Sulfate

    Science.gov (United States)

    Zhang, Xuejie; Ashby, Richard; Solaiman, Daniel K. Y.; Uknalis, Joseph; Fan, Xuetong

    2016-01-01

    Food contaminated with human pathogens, such as Salmonella spp. and Listeria monocytogenes, frequently causes outbreaks of foodborne illness. Consumer concern over the use of synthesized antimicrobials to enhance microbial food safety has led to a search of natural alternatives. The objectives of this study were to evaluate the antimicrobial activity of various types of sophorolipids (SLs) and thiamine dilauryl sulfate (TDS) against pathogenic Salmonella spp. and Listeria spp. Both free and lactonic forms of SLs were synthesized from Candida bombicola using palmitic, stearic, and oleic acids as co-feedstocks. TDS and purified SLs were used to treat cocktails of Salmonella spp. and Listeria spp. Results showed that lactonic SLs had higher antimicrobial activity than the free-acid form, and Gram-positive Listeria spp. were more susceptible to SLs and TDS than Gram-negative Salmonella spp. Listeria populations were reduced from an initial concentration of 7.2 log CFU/mL to a non-detectible level within a 1 min treatment of 0.1% (w/v) lactonic SLs and TDS in the presence of 20% ethanol, which itself did not significantly reduce the populations. There were no significant differences in the antimicrobial efficacy among palmitic, stearic, and oleic acid-based SLs against Salmonella or Listeria spp. Ethanol was utilized to improve the antimicrobial activity of free-acid SLs against Gram-negative bacteria. In general, TDS was more effective than the SLs against Salmonella and Listeria spp. scanning electron microscopy and transmission electron microscopy images showed that SLs and TDS damaged Listeria cell membranes and resulted in cell lysis. Overall, our results demonstrated that SLs and TDS in the presence of ethanol can be used to inactivate foodborne pathogens, especially Gram-positive bacteria. PMID:28066390

  10. Inactivation of Salmonella spp. and Listeria spp. by Palmitic, Stearic, and Oleic Acid Sophorolipids and Thiamine Dilauryl Sulfate.

    Science.gov (United States)

    Zhang, Xuejie; Ashby, Richard; Solaiman, Daniel K Y; Uknalis, Joseph; Fan, Xuetong

    2016-01-01

    Food contaminated with human pathogens, such as Salmonella spp. and Listeria monocytogenes, frequently causes outbreaks of foodborne illness. Consumer concern over the use of synthesized antimicrobials to enhance microbial food safety has led to a search of natural alternatives. The objectives of this study were to evaluate the antimicrobial activity of various types of sophorolipids (SLs) and thiamine dilauryl sulfate (TDS) against pathogenic Salmonella spp. and Listeria spp. Both free and lactonic forms of SLs were synthesized from Candida bombicola using palmitic, stearic, and oleic acids as co-feedstocks. TDS and purified SLs were used to treat cocktails of Salmonella spp. and Listeria spp. Results showed that lactonic SLs had higher antimicrobial activity than the free-acid form, and Gram-positive Listeria spp. were more susceptible to SLs and TDS than Gram-negative Salmonella spp. Listeria populations were reduced from an initial concentration of 7.2 log CFU/mL to a non-detectible level within a 1 min treatment of 0.1% (w/v) lactonic SLs and TDS in the presence of 20% ethanol, which itself did not significantly reduce the populations. There were no significant differences in the antimicrobial efficacy among palmitic, stearic, and oleic acid-based SLs against Salmonella or Listeria spp. Ethanol was utilized to improve the antimicrobial activity of free-acid SLs against Gram-negative bacteria. In general, TDS was more effective than the SLs against Salmonella and Listeria spp. scanning electron microscopy and transmission electron microscopy images showed that SLs and TDS damaged Listeria cell membranes and resulted in cell lysis. Overall, our results demonstrated that SLs and TDS in the presence of ethanol can be used to inactivate foodborne pathogens, especially Gram-positive bacteria.

  11. Significance of Ligand Exchange Relating to Sulfate in Retarding Acidification of Variable Charge Soils Caused by Acid Rain

    Institute of Scientific and Technical Information of China (English)

    WANGJINGHUA; YUTIANREN

    1996-01-01

    For the purpose of evaluating the role of ligand exchange of sulfate ions in retarding the rate of acidification of variable charge soils,the changes in pH after the addition of different amounts of HNO3 or H2SO4 to representative soils of China were measured .A difference between pH changes caused by the two kinds of acids was observed only for variable charge soils and kaolinite,but not for constant charge soils and bentonite,The larger the proportion of H2SO4 in the HNO3-H2SO4 mixture,the lower the calculated H+ ion activities remained in the suspension.The difference in H+ ion activities between H2SO4 systems and HNO3 systems was larger for soils with a low base-saturation(BS) percentage than those with a high BS percentage.The removal of free iron oxides from the soil led to a decrease in the difference,while the coating of Fe2O3 on a bentonite resulted in a remarkable appearance of the difference.The effect of ligand exchange on the acidity status of the soil varied with the soil type.Surface soils with a high organic matter content showed a less pronounced effect of ligand exchange than subsoils did.It was estimated that when acid rain chiefly containing H2SO4 was deposited on variable charge soils the acidification rate might be slower by 20%-40% than that when the acid rain chiefly contained HNO3 for soils with a high organic matter content,and that the rate might be half of that caused by HNO3 for soils with a low organic matter content,especially for latosols.

  12. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate

    Science.gov (United States)

    Obukhova, Elena N.; Mchedlov-Petrossyan, Nikolay O.; Vodolazkaya, Natalya A.; Patsenker, Leonid D.; Doroshenko, Andrey O.; Marynin, Andriy I.; Krasovitskii, Boris M.

    2017-01-01

    Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR+ ⇄ R + H+) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions. In this media, the form R exists as a zwitterion R±. The indices of apparent ionization constants of fifteen rhodamine cations HR+ with different substituents in the xanthene moiety vary within the range of pKaapp = 5.04 to 5.53. The distinct dependence of emission of rhodamines bound to micelles on pH of bulk water opens the possibility of using them as fluorescent interfacial acid-base indicators.

  13. Study on Extracting Rare Earth from Sulfate System by Long-Chain Fatty Acid

    Institute of Scientific and Technical Information of China (English)

    Xu Yanhui; Zhao Zengqi; Liu Quansheng

    2004-01-01

    The extraction of rare earths by long-chain fatty acid in kerosene from sulphate system was described.It was demonstrated from the experimental results that the ratio of kerosene: fatty acid: isooctanol = 55 : 30: 15 ( V/V),By the saturation capability method and the slope method, the extracted reaction mechanism of the extraction of rare earth was studied.It is shown that the extraction reaction conform to the cation exchange reaction mechanism.The extracted sequence of rare earth was determined in this system and it is shown that there is no tetrad effect and the position of yttrium is between lanthanum and cerium.

  14. Thermodynamic properties of multifunctional oxygenates in atmospheric aerosols from quantum mechanics and molecular dynamics: dicarboxylic acids.

    Science.gov (United States)

    Tong, Chinghang; Blanco, Mario; Goddard, William A; Seinfeld, John H

    2004-07-15

    Ambient particulate matter contains polar multifunctional oxygenates that partition between the vapor and aerosol phases. Vapor pressure predictions are required to determine the gas-particle partitioning of such organic compounds. We present here a method based on atomistic simulations combined with the Clausius-Clapeyron equation to predict the liquid vapor pressure, enthalpies of vaporization, and heats of sublimation of atmospheric organic compounds. The resulting temperature-dependent vapor pressure equation is a function of the heat of vaporization at the normal boiling point [deltaHvap(Tb)], normal boiling point (Tb), and the change in heat capacity (liquid to gas) of the compound upon phase change [deltaCp(Tb)]. We show that heats of vaporization can be estimated from calculated cohesive energy densities (CED) of the pure compound obtained from multiple sampling molecular dynamics. The simulation method (CED) uses a generic force field (Dreiding) and molecular models with atomic charges determined from quantum mechanics. The heats of vaporization of five dicarboxylic acids [malonic (C3), succinic (C4), glutaric (C5), adipic (C6), and pimelic (C7)] are calculated at 500 K. Results are in agreement with experimental values with an averaged error of about 4%. The corresponding heats of sublimation at 298 K are also predicted using molecular simulations. Vapor pressures of the five dicarboxylic acids are also predicted using the derived Clausius-Clapeyron equation. Predicted liquid vapor pressures agree well with available literature data with an averaged error of 29%, while the predicted solid vapor pressures at ambient temperature differ considerably from a recent study by Bilde et al. (Environ. Sci. Technol. 2003, 37, 1371-1378) (an average of 70%). The difference is attributed to the linear dependence assumption thatwe used in the derived Clausius-Clapeyron equation.

  15. Could Acid Sulfate Soils Be a Potential Environmental Threat to Estuarine Ecosystems on the South CHina Coast?

    Institute of Scientific and Technical Information of China (English)

    C.LIN

    1999-01-01

    Acid sulfate soils (ASS) contain considerable amounts of reduced sulfur compounds(mainly pyrite) which produce sulfuric acid upon their oxidation.ASS-derived environmental degradation widely occurs in the coastal lowlands around the world,especially in the tropical and subtropical areas.The presence of ASS iun the South China has been recognized but their distribution may be largely underestimated because the soil survey data concerning ASS are based on unreliable methods and techniques.ASS in the South China have been traditionally used for rice cultivation and this practice has been proved sustainable if appropriate improvement measures are adopted.Recently,the rapid economic growth in the region has resulted in intensified coastal development which frequently involves activities that may disturb ASS,Construction of roads,foundations and aquaculture ponds may cause the exposure of ASS to air and bring about severe environmental acidificvation.There is currently insufficient awareness of the problems among the researchers,policy-makers and land managers in the South China.More attention must be paid to the possible ASS-dervived environmental degradation in order to ensure a sustainable development of the coastal lowlands in the South China region.

  16. Stannous sulfate as an electrolyte additive for lead acid battery made from a novel ultrafine leady oxide

    Science.gov (United States)

    Wang, Qin; Liu, Jianwen; Yang, Danni; Yuan, Xiqing; Li, Lei; Zhu, Xinfeng; Zhang, Wei; Hu, Yucheng; Sun, Xiaojuan; Liang, Sha; Hu, Jingping; Kumar, R. Vasant; Yang, Jiakuan

    2015-07-01

    The effects of SnSO4 as an electrolyte additive on the microstructure of positive plate and electrochemical performance of lead acid battery made from a novel leady oxide are investigated. The novel leady oxide is synthesized through leaching of spent lead paste in citric acid solution. The novel leady oxides are used to prepare working electrode (WE) subjected to electrochemical cyclic voltammetry (CV) tests. Moreover, the novel leady oxides are used as active materials of positive plate assembled as a testing battery of 1.85 A h capacity. In CV tests, SEM/EDX results show that the major crystalline phase of the paste in WE after CV cycles is PbSO4. The larger column-shaped PbSO4 crystals easily generate in the paste of WE without an electrolyte additive of SnSO4. However, PbSO4 crystals significantly become smaller with the addition of SnSO4 in the electrolyte. In batteries testing, SEM results show that an electrolyte additive of SnSO4 could effectively decrease PbO2 particle size in the positive active materials of the teardown battery at the end of charging procedure. It is indicated that an electrolyte additive of SnSO4 could have a positive influence on restraining larger particles of irreversible sulfation in charge/discharge cycles of battery testing.

  17. Molecular composition of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

    Directory of Open Access Journals (Sweden)

    S. L. Mkoma

    2013-02-01

    Full Text Available Atmospheric aerosol samples of PM2.5 and PM10 were collected during the wet and dry seasons in 2011 from a rural site in Tanzania and analysed for water-soluble dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, and fatty acids using a gas chromatography/flame ionization detector (GC/FID and GC/mass spectrometry. Here we report the molecular composition and sources of diacids and related compounds for wet and dry seasons. Oxalic acid (C2 was found as the most abundant diacid species followed by succinic and/or malonic acids whereas glyoxylic acid and glyoxal were the dominant ketoacid and α-dicarbonyl, respectively in both seasons in PM2.5 and PM10. Mean concentration of C2 in PM2.5 (121 ± 47 ng m−3 was lower in wet season than dry season (258 ± 69 ng m−3. Similarly, PM10 samples showed lower concentration of C2 (169 ± 42 ng m−3 in wet season than dry season (292 ± 165 ng m−3. Relative abundances of C2 in total diacids were 65% and 67% in PM2.5 and 65% and 64% in PM10 in the wet and dry seasons, respectively. Total concentrations of diacids (289–362 ng m−3, ketoacids (37.8–53.7 ng m−3, and α-dicarbonyls (5.7–7.8 ng m−3 in Tanzania are higher than those reported at a rural background site in Nylsvley (South Africa but comparable or lower than those reported from sites in Asia and Europe. Diacids and ketoacids were found to be present mainly in PM2.5 in both seasons (total α-dicarbonyls in the dry season, suggesting a production of organic acids from pyrogenic sources and photochemical oxidations. Averaged contributions of total diacids to aerosol total carbon were 1.4% in PM2.5 and 2.1% in PM10 during wet season and 3.3% in PM2.5 and 3.9% in PM10 during

  18. Improved synthesis of glycine, taurine and sulfate conjugated bile acids as reference compounds and internal standards for ESI-MS/MS urinary profiling of inborn errors of bile acid synthesis.

    Science.gov (United States)

    Donazzolo, Elena; Gucciardi, Antonina; Mazzier, Daniela; Peggion, Cristina; Pirillo, Paola; Naturale, Mauro; Moretto, Alessandro; Giordano, Giuseppe

    2017-04-01

    Bile acid synthesis defects are rare genetic disorders characterized by a failure to produce normal bile acids (BAs), and by an accumulation of unusual and intermediary cholanoids. Measurements of cholanoids in urine samples by mass spectrometry are a gold standard for the diagnosis of these diseases. In this work improved methods for the chemical synthesis of 30 BAs conjugated with glycine, taurine and sulfate were developed. Diethyl phosphorocyanidate (DEPC) and diphenyl phosphoryl azide (DPPA) were used as coupling reagents for glycine and taurine conjugation. Sulfated BAs were obtained by sulfur trioxide-triethylamine complex (SO3-TEA) as sulfating agent and thereafter conjugated with glycine and taurine. All products were characterized by NMR, IR spectroscopy and high resolution mass spectrometry (HRMS). The use of these compounds as internal standards allows an improved accuracy of both identification and quantification of urinary bile acids. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    Directory of Open Access Journals (Sweden)

    S. Schobesberger

    2014-05-01

    Full Text Available The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3 and sulfuric acid (H2SO4. Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 2SO4] from 3.3 × 106 to 1.4 × 109 cm−3, and a temperature range from −25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4 only form at [NH3] / [H2SO4]3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm / Δn, where n is in the range 4–18 (negatively charged clusters or 1–17 (positively charged clusters. For negatively charged clusters, Δm / Δn saturated between 1 and 1.4 for [NH3] / [H2SO4]>10. Positively charged clusters grew on average by Δm / Δn = 1.05 and

  20. Characteristics and sources of formic, acetic and oxalic acids in PM 2.5 and PM 10 aerosols in Beijing, China

    Science.gov (United States)

    Wang, Ying; Zhuang, Guoshun; Chen, Shuang; An, Zhisheng; Zheng, Aihua

    2007-04-01

    Chemistry of formic, acetic and oxalic acids was studied at four sites representing the urban and rural conditions in Beijing from March 2002 to October 2003. The investigation was based on the PM 2.5 and PM 10 aerosols collected with virtual samplers. The total concentrations of these carboxylic acids averaged at 541 ng m - 3 in PM 2.5 and 615 ng m - 3 in PM 10, contributing 0.4% and 0.3% to the total mass of the aerosol, respectively. Oxalic acid was the most abundant carboxylic acids in aerosols. Formic and acetic acids displayed different seasonal variations (formic: spring summer > autumn > winter), and the variations of these acids were consistent among different sites in urban area. Formic and oxalic acids had a diurnal variation of nighttime waste/biomass burnings, cooking and secondary formation from anthropogenic or natural gas-phase precursors could be the major sources of these acids. Acetic-to-formic acid ratio (A/F) was used to distinguish the primary sources and the secondary sources, and it indicated that the contribution of the primary sources was higher at rural site than at urban sites. A new method was developed to study the contribution of the biomass burning to these acids, which was estimated to be 30-60% for formic and oxalic acids in aerosols.

  1. Multivariate analysis of electron detachment dissociation and infrared multiphoton dissociation mass spectra of heparan sulfate tetrasaccharides differing only in hexuronic acid stereochemistry.

    Science.gov (United States)

    Oh, Han Bin; Leach, Franklin E; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I Jonathan

    2011-03-01

    The structural characterization of glycosaminoglycan (GAG) carbohydrates by mass spectrometry has been a long-standing analytical challenge due to the inherent heterogeneity of these biomolecules, specifically polydispersity, variability in sulfation, and hexuronic acid stereochemistry. Recent advances in tandem mass spectrometry methods employing threshold and electron-based ion activation have resulted in the ability to determine the location of the labile sulfate modification as well as assign the stereochemistry of hexuronic acid residues. To facilitate the analysis of complex electron detachment dissociation (EDD) spectra, principal component analysis (PCA) is employed to differentiate the hexuronic acid stereochemistry of four synthetic GAG epimers whose EDD spectra are nearly identical upon visual inspection. For comparison, PCA is also applied to infrared multiphoton dissociation spectra (IRMPD) of the examined epimers. To assess the applicability of multivariate methods in GAG mixture analysis, PCA is utilized to identify the relative content of two epimers in a binary mixture.

  2. 酸性硫酸钙杀菌性能试验研究%Study on germicidal efficacy of acidic calcium sulfate

    Institute of Scientific and Technical Information of China (English)

    王劲; 于礼; 刘国栋; 肖潇; 佟颖

    2017-01-01

    目的 研究酸性硫酸钙消毒相关性能,为实际应用提供依据.方法 采用载体浸泡定量杀菌试验方法,对该酸性硫酸钙杀灭微生物效果与稳定性进行观察.结果 该酸性硫酸钙为一种强酸性溶液,400倍稀释液的pH值仍<1.0.以100倍稀释液作用4 min,对载体上金黄色葡萄球菌、大肠杆菌的平均杀灭对数值均>3.0;对白色念珠菌无明显杀菌效果.经室温自然存放24个月后其杀菌性能稳定.结论 该酸性硫酸钙对载体表面细菌繁殖体有较好的杀菌效果,且稳定性好.%Objective To study the germicidal efficacy of acidic calcium sulfate and to provide the basis for practical application.Methods The carrier quantitative germicidal test was used to observe the germicidal efficacy of acidic calcium sulfate and to study its stability after storing under different conditions.Results The acidic calcium sulfate showed strong acidity and the pH of 400 times dilution was still less than 1.0.The average killing logarithm values of Escherichia coli and Staphylococcus exposed to 100 times dilution of acidic calcium sulfate for 4 min were all above 3.0,while the acidic calcium sulfate showed no obvious germicidal efficacy on Candida albicans.No significant difference in the average killing logarithm values was found after storing at room temperature for 24 months.Conclusion Acidic calcium sulfate has a value of practical application because of its good germicidal efficacy to bacteria on the carrier and good stability.

  3. Aerosol probes of emphysema progression in dogs treated with all trans retinoic acid--an exploratory study.

    Science.gov (United States)

    Rosenthal, Frank S

    2007-01-01

    This study used aerosol probes and lung function tests to investigate whether all trans retinoic acid (RA) can reverse experimental emphysema in dogs. Three dogs were evaluated with lung mechanics tests, including inspiratory capacity (IC), total lung capacity (TLC), and the ratio of forced expired volume in 0.5 sec to forced vital capacity (FEV0.5/FVC), an aerosol-derived measure of pulmonary airspace size (effective airspace diameter, EAD), and an aerosol-derived measure of nonuniform ventilation (aerosol dispersion, AD). Emphysema was induced by exposure to aerosolized papain. At 11 or 12 weeks post-papain exposure, dogs received oral RA (2 mg/kg/day) for 8 weeks, and were followed for an additional 4 weeks after stopping RA treatment. In all dogs, lung injury increased in the first 11-12 weeks following papain exposure, as evidenced by increasing trends of inspiratory capacity IC, TLC, EAD, and AD, and a decreasing trend of FEV0.5/FVC. These parameters of lung injury partially and transiently reversed their trends between 2 and 6 weeks following the initiation of RA treatment. A sham RA-treated group was not studied. However, similar reversals of lung injury were not seen in a previous study of dogs treated with papain but not RA, suggesting that RA altered emphysema progression in the current study. The limited reversal of lung injury in this study contrasts with more pronounced treatment effects seen in previous studies with rats. This paper discusses possible reasons for differences in these studies, as well as suggestions for improved experimental investigations of emphysema therapies.

  4. Strategy Approach for Direct Enantioseparation of Hyoscyamine Sulfate and Zopiclone on a Chiral αl-Acid Glycoprotein Column and Determination of Their Eutomers: Thermodynamic Study of Complexation.

    Science.gov (United States)

    Zaazaa, Hala E; Salama, Nahla N; Abd El Halim, Lobna M; Salem, Maissa Y; Abd El Fattah, Laila E

    2016-01-01

    Rapid and simple isocratic high-performance liquid chromatographic methods with UV detection were developed and validated for the direct resolution of racemic mixtures of hyoscyamine sulfate and zopiclone. The method involved the use of αl -acid glycoprotein (AGP) as chiral stationary phase. The stereochemical separation factor (ά) and the stereochemical resolution factor (Rs ) obtained were 1.29 and 1.60 for hyoscyamine sulfate and 1.47 and 2.45 for zopiclone, respectively. The method was used for determination of chiral switching (eutomer) isomers: S-hyoscyamine sulfate and eszopiclone. Several mobile phase parameters were investigated for controlling enantioselective retention and resolution on the chiral AGP column. The influence of mobile phase, concentration and type of uncharged organic modifier, ionic strength, and column temperature on enantioselectivity were studied. Calibration curves were linear in the ranges of 1-10 µg mL(-1) and 0.5-5 µg mL(-1) for S-hyoscyamine sulfate and eszopiclone, respectively. The method is specific and sensitive, with lower limits of detection and quantifications of 0.156, 0.515 and 0.106, 0.349 for S-hyoscyamine sulfate and eszopiclone, respectively. The method was used to identify quantitatively the enantiomers profile of the racemic mixtures of the studied drugs in their pharmaceutical preparations. Thermodynamic studies were performed to calculate the enthalpic ΔH and entropic ΔS terms. The results showed that enantiomer separation of the studied drugs were an enthalpic process.

  5. Seasonal and diurnal characteristics of water soluble inorganic compounds in the gas and aerosol phase in the Zurich area

    Directory of Open Access Journals (Sweden)

    R. Fisseha

    2006-01-01

    Full Text Available Gas and aerosol samples were taken using a wet effluent diffusion denuder/aerosol collector (WEDD/AC coupled to ion chromatography (IC in the city of Zurich, Switzerland from August to September 2002 and in March 2003. Major water soluble inorganic ions; nitrate, sulfate, and nitrite were analyzed online with a time resolution of two hours for the gas and aerosol phase. The fraction of water soluble inorganic anions in PM10 varied from 15% in August to about 38% in March. Seasonal and diurnal variations of nitrate in the gas and aerosol phase were observed with more than 50% of the total nitrate in the gas phase during August and more than 80% of nitrate in the aerosol phase during March exceeding the concentration of sulfate by a factor of 2. Aerosol sulfate, on the other hand, did not show significant variability with season. However, in the gas phase, the SO2 concentration was 6.5 times higher in winter than in summer. Nitrous acid (HONO also showed a diurnal variation in both the gas and aerosol phase with the lowest concentration (0.2–0.6 µg/m3 in the afternoon. The primary pollutants, NO, CO and SO2 mixing ratios were often at their highest between 04:00–10:00 local time due to the build up of fresh vehicle emission under a nocturnal inversion.

  6. Different pathways of canalicular secretion of sulfated and non-sulfated fluorescent bile acids : a study in isolated hepatocyte couplets and TR- rats

    NARCIS (Netherlands)

    Mills, CO; Milkiewicz, P; Muller, M; Roma, MG; Havinga, R; Coleman, R; Kuipers, F; Jansen, PLM; Elias, E

    1999-01-01

    Background/Aims: Fluorescent bile acids have proved useful for characterizing bile salt transport mechanisms, The aim of this study was to further validate the use of lysyl-fluorescein conjugated bile acid analogues as surrogate bile acids, Methods: We analyzed biliary excretion kinetics of cholyl l

  7. Heparan sulfate biosynthesis

    DEFF Research Database (Denmark)

    Multhaupt, Hinke A B; Couchman, John R

    2012-01-01

    Heparan sulfate is perhaps the most complex polysaccharide known from animals. The basic repeating disaccharide is extensively modified by sulfation and uronic acid epimerization. Despite this, the fine structure of heparan sulfate is remarkably consistent with a particular cell type. This suggests...... that the synthesis of heparan sulfate is tightly controlled. Although genomics has identified the enzymes involved in glycosaminoglycan synthesis in a number of vertebrates and invertebrates, the regulation of the process is not understood. Moreover, the localization of the various enzymes in the Golgi apparatus has......-quality resolution of the distribution of enzymes. The EXT2 protein, which when combined as heterodimers with EXT1 comprises the major polymerase in heparan sulfate synthesis, has been studied in depth. All the data are consistent with a cis-Golgi distribution and provide a starting point to establish whether all...

  8. General Motors sulfate dispersion experiment: summary of EPA measurements

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, W.E. (Environmental Protection Agency, Washington, DC); Spiller, L.L.; Ellestad, T.G.

    1977-01-01

    In October 1975, General Motors sponsored a study of sulfate exposures utilizing a fleet of catalyst equipped motor vehicles in controlled, simulated, highway driving conditions. This paper reports some EPA sponsored measurements. Sulfuric acid aerosol, in the Aitken nuclei mode, geometric mean diameter (GMD) of about 0.02 ..mu..m, is emitted in the exhaust of catalyst equipped vehicles. Measurement of sulfuric acid 20 m downwind of the roadway indicated a lack of complete neutralization by ammonia. When the wind was perpendicular to the roadway there was little coagulation of sulfuric acid into the accumulation mode, GMD of about 0.24 ..mu..m. From measurement of the mass flow rate of aerosol sulfur from the simulated freeway, the aerosol sulfur emission rate per car was determined to be 3.5 +- 0.8 ..mu..g/m (5.6 +- 1.3 mg/mile) corresponding to a 12 +- 3 percent conversion of fuel sulfur into emitted aerosol sulfur.

  9. Spatio-temporal distributions of dicarboxylic acids, ω-oxocarboxylic acids, pyruvic acid, α-dicarbonyls and fatty acids in the marine aerosols from the North and South Pacific

    Science.gov (United States)

    Hoque, Mir Md. Mozammal; Kawamura, Kimitaka; Uematsu, Mitsuo

    2017-03-01

    Aerosol samples (TSP) were collected during a cruise in the North (3°05‧N-34°02‧N) and South (6°59‧S-25°46‧S) Pacific to investigate the spatio-temporal distributions of water-soluble dicarboxylic acids and related compounds. The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and then succinic (C4) acid. However, we found a predominance of C4 over C3 in the aerosol sample that was collected in the western North Pacific Rim with a heavy influence from continental air masses. Atmospheric abundances of short chain diacids (C2-C4) are 2-3 times higher in the North Pacific than in the South Pacific. During the cruise, abundances of C2 in the western North Pacific are 5 times higher than those in the rest of the samples collected. Moreover, the aerosol samples collected in the western North Pacific demonstrated that glyoxylic (ωC2) acid and methylglyoxal (MeGly) were dominant together with C2. We found a strong correlation between C2 and ωC2 (r = 0.87) and C2 and MeGly (r = 0.97) in the western North Pacific aerosols but the correlations are significantly weak in the samples from the central North Pacific and Southern Ocean. Diacids were found to account for 1.6 to 14% of organic carbon with higher values in the western North Pacific. These results, together with 7-day backward air mass trajectories, indicate that ωC2 and MeGly are both originated from the photochemical oxidation of continent-derived organic precursors including isoprene, which can serve as precursors for the production of C2 during long-range atmospheric transport.

  10. 21 CFR 184.1307 - Ferric sulfate.

    Science.gov (United States)

    2010-04-01

    ... Substances Affirmed as GRAS § 184.1307 Ferric sulfate. (a) Ferric sulfate (iron (III) sulfate, Fe2(SO4)3 CAS Reg. No. 10028-22-5) is a yellow substance that may be prepared by oxidizing iron (II) sulfate or by treating ferric oxide or ferric hydroxide with sulfuric acid. (b) The ingredient must be of a...

  11. Fine aerosol bulk composition measured on WP-3D research aircraft in vicinity of the Northeastern United States – results from NEAQS

    Directory of Open Access Journals (Sweden)

    C. Warneke

    2007-02-01

    Full Text Available During the New England Air Quality Study (NEAQS in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC of the submicron (PM1.0 aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S. and Canada was predominately sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg−1 and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar within the boundary layer (altitude less than ~2.5 km, but was significantly higher in the free troposphere (above ~2.5 km. A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were largely comprised of organic aerosol components

  12. Enhanced concentrations of citric acid in spring aerosols collected at the Gosan background site in East Asia

    Science.gov (United States)

    Jung, Jinsang; Kawamura, Kimitaka

    2011-09-01

    In order to investigate water-soluble dicarboxylic acids and related compounds in the aerosol samples under the Asian continent outflow, total suspended particle (TSP) samples ( n = 32) were collected at the Gosan site in Jeju Island over 2-5 days integration during 23 March-1 June 2007 and 16-24 April 2008. The samples were analyzed for water-soluble dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls using a capillary gas chromatography technique. We found elevated concentrations of atmospheric citric acid (range: 20-320 ng m -3) in the TSP samples during mid- to late April of 2007 and 2008. To specify the sources of citric acid, dicarboxylic acids and related compounds were measured in the pollen sample collected at the Gosan site (Pollen_Gosan), authentic pollen samples from Japanese cedar ( Cryptomeria) (Pollen_cedar) and Japanese cypress ( Chamaecyparis obtusa) (Pollen_cypress), and tangerine fruit produced from Jeju Island. Citric acid (2790 ng in unit mg of pollen mass) was found as most abundant species in the Pollen_Gosan, followed by oxalic acid (2390 ng mg -1). Although citric acid was not detected in the Pollen_cedar and Pollen_cypress as major species, it was found as a dominant species in the tangerine juice while malic acid was detected as major species in the tangerine peel, followed by oxalic and citric acids. Since Japanese cedar trees are planted around tangerine farms to prevent strong winds from the Pacific Ocean, citric acid that may be directly emitted from tangerine is likely adsorbed on pollens emitted from Japanese cedar and then transported to the Gosan site. Much lower malic/citric acid ratios obtained under cloudy condition than clear condition suggest that malic acid may rapidly decompose to lower molecular weight compounds such as oxalic and malonic acids (

  13. Excretion of 3-Mercaptolactate-Cysteine Disulfide, Sulfate and Taurine in human Urine before and after Oral Administration of Sulfur-containing Amino Acids.

    Directory of Open Access Journals (Sweden)

    Yuasa,Shigeki

    1990-06-01

    Full Text Available The excretion of 3-mercaptolactate-cysteine mixed disulfide [S-(2-hydroxy-2-carboxyethylthio-L-cysteine, HCETC], sulfate and taurine in the urine of normal adults was investigated before and after oral administration of L-cysteine and related sulfur-containing amino acids. Before the loading of amino acids, the excretion (mean +/- SD per kg of body weight per day of HCETC, free sulfate and taurine was 0.096 +/- 0.042, 305.7 +/- 66.1 and 31.9 +/- 8.7 mumols, respectively. After the loading of L-cysteine (800 mumols/kg of body weight, the average excretion in the 24-h urine of HCETC increased 2-fold and that of taurine increased 1.6-fold. The average excretion of free sulfate after the L-cysteine loading was 989.4 +/- 145.1 and 388.8 +/- 51.6 mumols/kg per day in the first and second 24-h urine, respectively, indicating that the sulfur corresponding to 85% of the L-cysteine loaded was excreted as free sulfate in 24 h. Administration of L-cystine (400 mumols/kg resulted in similar results. The increase in HCETC after L-cysteine or L-cystine administration indicates that L-cysteine is metabolized in part through the transamination pathway (3-mercaptopyruvate pathway and that an equilibrium exists between the intake and excretion of sulfur in humans.

  14. Spray Dried Aerosol Particles of Pyrazinoic Acid Salts for Tuberculosis Therapy. [Corrected].

    Science.gov (United States)

    Durham, P G; Zhang, Y; German, N; Mortensen, N; Dhillon, J; Mitchison, D A; Fourie, P B; Hickey, A J

    2015-08-03

    Tuberculosis is the most serious infectious disease caused by a single organism, Mycobacterium tuberculosis (Mtb). The standard of care is a protracted and complex drug treatment regimen made more complicated and of longer duration by the incidence of multiple and extensively drug resistant disease. Pulmonary delivery of aerosols as a supplement to the existing regimen offers the advantage of delivering high local drug doses to the initial site of infection and most prominent organ system involved in disease. Pyrazinamide is used in combination with other drugs to treat tuberculosis. It is postulated that the action of pyrazinoic acid (POA), the active moiety of pyrazinamide, may be enhanced by local pH adjustment, when presented as a salt form. POA was prepared as leucine (POA-leu) and ammonium salts (POA-NH4), spray dried, and characterized in terms of physicochemical properties (melting point, crystallinity, moisture content), aerodynamic performance (aerodynamic particle size distribution, emitted dose), and in vitro inhibitory effect on two mycobacteria (Mtb and Mycobacterium bovis). Particles were prepared in sizes suitable for inhalation (3.3 and 5.4 μm mass median aerodynamic diameter and 61 and 40% of the aerodynamic particle size distribution less than 4.46 μm, as measured by inertial impaction, for POA-leu and POA-NH4, respectively) and with properties (stoichiometric 1:1 ratio of salt to drug, melting points at ∼180 °C, with water content of <1%) that would support further development as an inhaled dosage form. In addition, POA salts demonstrated greater potency in inhibiting mycobacterial growth compared with POA alone, which is promising for therapy.

  15. Comparison of Sodium Acid Sulfate and UV-C Treatment on Browning and Storage Quality of Fresh-Cut Potatoes

    Directory of Open Access Journals (Sweden)

    Yajing Xie

    2017-01-01

    Full Text Available Fresh-cut vegetables, such as potato chips, get brown quickly and can easily be infected by bacterium during storage. Sodium acid sulfate (SAS and UV-C treatments are regarded as effective methods for food preservation. In this study, the effects of SAS, UV-C treatment, and their combination on fresh-cut potatoes during storage were evaluated. Compared with the control, all of the treatments were effective in inhibiting the bacterial growth during the whole storage period. Also, both SAS and SAS + UV-C treatments significantly decreased browning and polyphenol oxidase (PPO activity and increased the firmness and malondialdehyde (MDA contents, while the UV-C treatment has no good effects on protecting such storage qualities in fresh-cut potatoes. However, when compared with SAS treatment, the combination of SAS and UV-C treatment did not promote the effect in protecting the storage abilities. Thus, it was concluded that SAS is a better treatment in extending shelf life and controlling the quality of fresh-cut potatoes during storage compared to UV-C treatment.

  16. Occurrence and role of algae and fungi in acid mine drainage environment with special reference to metals and sulfate immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Das, B.K.; Roy, A.; Koschorreck, M.; Mandal, S.M.; Wendt-Potthoff, K.; Bhattacharya, J. [Indian Institute for Technology, Kharagpur (India). Dept. of Mining Engineering

    2009-03-15

    Passive remediation of Acid Mine Drainage (AMD) is a popular technology under development in current research. Roles of algae and fungi, the natural residents of AMD and its attenuator are not emphasized adequately in the mine water research. Living symbiotically various species of algae and fungi effectively enrich the carbon sources that help to maintain the sulfate reducing bacterial (SRB) population in predominantly anaerobic environment. Algae produce anoxic zone for SRB action and help in biogenic alkalinity generation. While studies on algal population and actions are relatively available those on fungal population are limited. Fungi show capacity to absorb significant amount of metals in their cell wall, or by extracellular polysaccharide slime. This review tries to throw light on the roles of these two types of microorganisms and to document their activities in holistic form in the mine water environment. This work, inter alia, points out the potential and gap areas of likely future research before potential applications based on fungi and algae initiated AMD remediation can be made on sound understanding.

  17. Effect of ferrous sulfate and nitrohumic acid neutralization on the leaching of metals from a combined bauxite residue.

    Science.gov (United States)

    Ren, Jie; Liu, Jidong; Chen, Juan; Liu, Xiaolian; Li, Fasheng; Du, Ping

    2017-04-01

    Bauxite residue neutralization is intended to open opportunities for revegetation and reuse of the residue. Ferrous sulfate (FS) and nitrohumic acid (NA) were two kinds of materials studied for pH reduction of the residue from 10.6 to 8.3 and 8.1, respectively. The effects of FS and NA on the leaching of metals from a combined bauxite residue were investigated by using sequential and multiple extraction procedures. Neutralization with FS and NA restricted the leaching of Al, V, and Pb from the residue but promoted the leaching of Fe, Cu, Mn, and Ni, consistent with the changes in the potentially mobile fractions. With the exceptions of Pb and Ni, leaching of metals increased during a 10-day extraction period. However, the maximum leaching of Al, V, Pb, Fe, Cu, Mn, and Ni from neutralized bauxite residue were 0.46 mg/L, 59.3, 12.9, 167, 95.3, 15.5, and 14.5 μg/L, respectively, which were under the corresponding limits in the National Standard (GB/T 14848-93). Although it is necessary to consider the continued leaching of metals during neutralization, both maximum and accumulation leaching concentrations of metals from a combined bauxite residue were too low to pose a potential environmental risk.

  18. The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol

    Directory of Open Access Journals (Sweden)

    V. Soonsin

    2010-08-01

    Full Text Available We present vapor pressure data of the C2 to C5 dicarboxylic acids deduced from measured evaporation rates of single levitated particles as both, aqueous droplets and solid crystals. The data of aqueous solution particles over a wide concentration range allow us to directly calculate activities of the dicarboxylic acids and comparison of these activities with parameterizations reported in the literature. The data of the pure liquid state acids, i.e. the dicarboxylic acids in their supercooled melt state, exhibit no even-odd alternation in vapor pressure, while the acids in the solid form do. This observation is consistent with the known solubilities of the acids and our measured vapor pressures of the supercooled melt. Thus, the gas/particle partitioning of the different dicarboxylic acids in the atmosphere depends strongly on the physical state of the aerosol phase, the difference being largest for the even acids.

    Our results show also that, in general, measurements of vapor pressures of solid dicarboxylic acids may be compromised by the presence of amorphous fractions, polymorphic forms, crystalline structures with a high defect number, and/or solvent inclusions in the solid material, yielding a higher vapor pressure than the one of the thermodynamically stable crystalline form at the same temperature.

  19. The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol

    Directory of Open Access Journals (Sweden)

    V. Soonsin

    2010-12-01

    Full Text Available We present vapor pressure data of the C2 to C5 dicarboxylic acids deduced from measured evaporation rates of single levitated particles as both, aqueous droplets and solid crystals. The data of aqueous solution particles over a wide concentration range allow us to directly calculate activities of the dicarboxylic acids and comparison of these activities with parameterizations reported in the literature. The data of the pure liquid state acids, i.e. the dicarboxylic acids in their supercooled melt state, exhibit no even-odd alternation in vapor pressure, while the acids in the solid form do. This observation is consistent with the known solubilities of the acids and our measured vapor pressures of the supercooled melt. Thus, the gas/particle partitioning of the different dicarboxylic acids in the atmosphere depends strongly on the physical state of the aerosol phase, the difference being largest for the even acids. Our results show also that, in general, measurements of vapor pressures of solid dicarboxylic acids may be compromised by the presence of polymorphic forms, crystalline structures with a high defect number, and/or solvent inclusions in the solid material, yielding a higher vapor pressure than the one of the thermodynamically stable crystalline form at the same temperature.

  20. Atmospheric aerosol compositions in China: spatial/temporal variability, chemical signature, regional haze distribution and comparisons with global aerosols

    Directory of Open Access Journals (Sweden)

    X. Y. Zhang

    2012-01-01

    Full Text Available From 2006 to 2007, the daily concentrations of major inorganic water-soluble constituents, mineral aerosol, organic carbon (OC and elemental carbon (EC in ambient PM10 samples were investigated from 16 urban, rural and remote sites in various regions of China, and were compared with global aerosol measurements. A large difference between urban and rural chemical species was found, normally with 1.5 to 2.5 factors higher in urban than in rural sites. Optically-scattering aerosols, such as sulfate (~16%, OC (~15%, nitrate (~7%, ammonium (~5% and mineral aerosol (~35% in most circumstance, are majorities of the total aerosols, indicating a dominant scattering feature of aerosols in China. Of the total OC, ~55%–60% can be attributed to the formation of the secondary organic carbon (SOC. The absorbing aerosol EC only accounts for ~3.5% of the total PM10. Seasonally, maximum concentrations of most aerosol species were found in winter while mineral aerosol peaks in spring. In addition to the regular seasonal maximum, secondary peaks were found for sulfate and ammonium in summer and for OC and EC in May and June. This can be considered as a typical seasonal pattern in various aerosol components in China. Aerosol acidity was normally neutral in most of urban areas, but becomes some acidic in rural areas. Based on the surface visibility observations from 681 meteorological stations in China between 1957 and 2005, four major haze areas are identified with similar visibility changes, namely, (1 Hua Bei Plain in N. China, and the Guanzhong Plain; (2 E. China with the main body in the Yangtze River Delta area; (3 S. China with most areas of Guangdong and the Pearl River Delta area; (4 The Si Chuan Basin in S.W. China. The degradation of visibility in these areas is linked with the emission changes and high PM concentrations. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric

  1. Mechanism of electrochemical reduction of hydrogen peroxide on copper in acidic sulfate solutions.

    Science.gov (United States)

    Stewart, Karen L; Gewirth, Andrew A

    2007-09-11

    Hydrogen peroxide is a commonly used oxidizer component in chemical mechanical planarization slurries, used in the processing of Cu metallization in microelectronics applications. We studied the electrochemical reduction of hydrogen peroxide on Cu in 0.1 M H2SO4 solutions using methods including cyclic voltammetry, rotating disk electrode experiments, surface-enhanced Raman spectroscopy, and density functional theory (DFT) calculations. The spectroscopy reveals that the hydrogen peroxide molecule is reduced at negative potentials to form a Cu-OH surface species in acidic solutions, a result consistent with the insight from Tafel slope measurements. DFT calculations support the instability of peroxide relative to the surface-coordinated hydroxide on both Cu(111) and Cu(100) surfaces.

  2. Artificial primary marine aerosol production: a laboratory study with varying water temperature, salinity and succinic acid concentration

    Directory of Open Access Journals (Sweden)

    J. Zábori

    2012-08-01

    Full Text Available Primary marine aerosols are an important component of the climate system, especially in the remote marine environment. With diminishing sea-ice cover, better understanding of the role of sea spray aerosol on climate in the polar regions is required. As for Arctic Ocean water, laboratory experiments with NaCl water confirm that a few degrees change in the water temperature (Tw gives a large change in the number of primary particles. Smaller particles with a dry diameter between 0.01 μm and 0.25 μm dominate the aerosol number density, but their relative dominance decreases with increasing water temperature from 0 °C where they represent 85–90% of the total aerosol number to 60–70% of the total aerosol number at 10 °C water temperature. This effect is most likely related to a change in physical properties and not to modification of sea water chemistry. A change of salinity between 15 g kg−1 and 35 g kg−1 showed no influence on the relative shape of a particle number size distribution, nor did a change in water temperature between 0 °C and 16 °C. An experiment where succinic acid was added to a NaCl water solution showed, that the number concentration of particles with Dp < 0.312 μm decreased by 43% when the succinic acid concentration in NaCl water at Tw = 0 °C was increased from 0 μmol l−1 to 2446 μmol l−1. Different organic constituents and perhaps inorganic substances resulted in a particle number shift towards larger particle sizes, when comparing a size distribution resulting from pure NaCl water to size distributions resulting from Arctic Ocean water and resulting from NaCl water with a succinic acid concentration of 2446 μmol l−1.

  3. CCN Activation Properties of Multiple-Component, Smog Chamber Generated, and Ambient Aerosols

    Science.gov (United States)

    Raymond, T. M.; Pandis, S. N.

    2002-12-01

    Ambient aerosols are a complex mixture of inorganic and hundreds of organic compounds varying in structure and physical properties. Despite the considerable fraction of organic matter in atmospheric aerosol, relatively little is known about the ability of complex, mixed particles to act as cloud condensation nuclei (CCN). Previous work has focused on pure-component and dual-component aerosols and theoretical modeling of their activation. This work expands the investigation by studying the CCN-forming ability of multiple-component organic-inorganic mixed aerosol compounds produced in a smog chamber, and ambient aerosols. The CCN properties of aerosols produced in an indoor five cubic meter Teflon smog chamber and ambient aerosol are investigated experimentally combining a Tandem Differential Mobility Analyzer (TDMA) with a static diffusion CCN counter (M1 Model, DH Associates). Data was obtained for ozone oxidation products of alpha-pinene, beta-pinene, limonene, gasoline, and diesel fuel. Multiple-component aerosols were produced from atomizing a mixed solution of chemical components and studying the particles with the TDMA-CCNC system. Mixtures included ammonium sulfate, sodium chloride, pinonic acid, pinic acid, norpinic acid, glutamic acid, and leucine. Studies were performed at supersaturations of 0.3% and 1.0% with dry particle diameters ranging from 0.02 to 0.2 micrometers. The results were analyzed to gain insights into CCN properties of atmospheric aerosols composed of known mixtures of inorganic and organic species, mixed oxidation products of primary organic species, and actual ambient aerosols. The results are compared to the behavior of pure organic aerosols and theory.

  4. Gamma ray-induced synthesis of hyaluronic acid/chondroitin sulfate-based hydrogels for biomedical applications

    Science.gov (United States)

    Zhao, Linlin; Gwon, Hui-Jeong; Lim, Youn-Mook; Nho, Young-Chang; Kim, So Yeon

    2015-01-01

    Hyaluronic acid (HA)/chondroitin sulfate (CS)/poly(acrylic acid) (PAAc) hydrogel systems were synthesized by gamma-ray irradiation without the use of additional initiators or crosslinking agents to achieve a biocompatible hydrogel system for skin tissue engineering. HA and CS derivatives with polymerizable residues were synthesized. Then, the hydrogels composed of glycosaminoglycans, HA, CS, and a synthetic ionic polymer, PAAc, were prepared using gamma-ray irradiation through simultaneous free radical copolymerization and crosslinking. The physicochemical properties of the HA/CS/PAAc hydrogels having various compositions were investigated to evaluate their feasibility as artificial skin substitutes. The gel fractions of the HA/CS/PAAc hydrogels increased in absorbed doses up to 15 kGy, and they exhibited 91-93% gel fractions under 15 kGy radiation. All of the HA/CS/PAAc hydrogels exhibited relatively high water contents of over 90% and reached an equilibrium swelling state within 24 h. The enzymatic degradation kinetics of the HA/CS/PAAc hydrogels depended on both the concentration of the hyaluronidase solution and the ratio of HA/CS/PAAc. The in vitro drug release profiles of the HA/CS/PAAc hydrogels were significantly influenced by the interaction between the ionic groups in the hydrogels and the ionic drug molecules as well as the swelling of the hydrogels. From the cytotoxicity results of human keratinocyte (HaCaT) cells cultured with extracts of the HA/CS/PAAc hydrogels, all of the HA/CS/PAAc hydrogel samples tested showed relatively high cell viabilities of more than 82%, and did not induce any significant adverse effects on cell viability.

  5. Influence of chondroitin sulfate and hyaluronic acid on structure, mechanical properties, and glioma invasion of collagen I gels.

    Science.gov (United States)

    Yang, Ya-li; Sun, Charles; Wilhelm, Matthew E; Fox, Laura J; Zhu, Jieling; Kaufman, Laura J

    2011-11-01

    To mimic the extracellular matrix surrounding high grade gliomas, composite matrices composed of either acid-solubilized (AS) or pepsin-treated (PT) collagen and the glycosaminoglycans chondroitin sulfate (CS) and hyaluronic acid (HA) are prepared and characterized. The structure and mechanical properties of collagen/CS and collagen/HA gels are studied via confocal reflectance microscopy (CRM) and rheology. CRM reveals that CS induces fibril bundling and increased mesh size in AS collagen but not PT collagen networks. The presence of CS also induces more substantial changes in the storage and loss moduli of AS gels than of PT gels, in accordance with expectation based on network structural parameters. The presence of HA significantly reduces mesh size in AS collagen but has a smaller effect on PT collagen networks. However, both AS and PT collagen network viscoelasticity is strongly affected by the presence of HA. The effects of CS and HA on glioma invasion is then studied in collagen/GAG matrices with network structure both similar to (PT collagen-based gels) and disparate from (AS collagen-based gels) those of the corresponding pure collagen matrices. It is shown that CS inhibits and HA has no significant effect on glioma invasion in 1.0 mg/ml collagen matrices over 3 days. The inhibitory effect of CS on glioma invasion is more apparent in AS than in PT collagen gels, suggesting invasive behavior in these environments is affected by both biochemical and network morphological changes induced by GAGs. This study is among the few efforts to differentiate structural, mechanical and biochemical effects of changes to matrix composition on cell motility in 3D.

  6. Systematic Review and Meta-Analysis of Intravesical Hyaluronic Acid and Hyaluronic Acid/Chondroitin Sulfate Instillation for Interstitial Cystitis/Painful Bladder Syndrome

    Directory of Open Access Journals (Sweden)

    Jung-Soo Pyo

    2016-09-01

    Full Text Available Background/Aims: To assess the efficacy of intravesical hyaluronic acid (HA and HA/chondroitin sulfate (CS instillation in patients with interstitial cystitis/painful bladder syndrome by systematic review and meta-analysis. Methods: A systematic literature search was performed using the keywords: ‘interstitial cystitis' or ‘painful bladder syndrome' or ‘bladder pain syndrome' and ‘hyaluronic acid', up to March 31, 2016. The primary outcome was visual analogue scale related pain symptom (VAS. Secondary outcomes were the O'Leary-Sant Interstitial Cystitis Symptom Index (ICSI and Problem Index (ICPI, frequency, nocturia, bladder volume, and voided urine volume. Results: Ten articles involving 390 patients were retrieved and assessed in analysis. A significant improvement in mean VAS on fixed-effect and random-effect models (mean difference [MD] -3.654, 95% confidence interval [CI] -3.814 to -3.495, and MD -3.206, 95% CI -4.156 to -2.257, respectively was found. Significant improvements were found in the ICSI (MD -3.223, 95% CI -4.132 to -2.315 and ICPI (MD -2.941, 95% CI -3.767 to -2.116. Similarly, the other outcomes were significantly improved. Conclusion: Intravesical HA and HA/CS instillation improved pain symptom, quality of life, and other outcomes and could be included as therapeutic modality of interstitial cystitis/painful bladder syndrome.

  7. Solid-solution partitioning and thionation of diphenylarsinic acid in a flooded soil under the impact of sulfate and iron reduction.

    Science.gov (United States)

    Zhu, Meng; Tu, Chen; Hu, Xuefeng; Zhang, Haibo; Zhang, Lijuan; Wei, Jing; Li, Yuan; Luo, Yongming; Christie, Peter

    2016-11-01

    Diphenylarsinic acid (DPAA) is a major organic arsenic (As) compound derived from abandoned chemical weapons. The solid-solution partitioning and transformation of DPAA in flooded soils are poorly understood but are of great concern. The identification of the mechanisms responsible for the mobilization and transformation of DPAA may help to develop effective remediation strategies. Here, soil and Fe mineral incubation experiments were carried out to elucidate the partitioning and transformation of DPAA in anoxic (without addition of sulfate or sodium lactate) and sulfide (with the addition of sulfate and sodium lactate) soil and to examine the impact of sulfate and Fe(III) reduction on these processes. Results show that DPAA was more effectively mobilized and thionated in sulfide soil than in anoxic soil. At the initial incubation stages (0-4weeks), 6.7-74.5% of the total DPAA in sulfide soil was mobilized likely by sorption competition with sodium lactate. At later incubation stage (4-8weeks), DPAA was almost completely released into the solution likely due to the near-complete Fe(III) reduction. Scanning transmission X-ray microscopy (STXM) results provide further direct evidence of elevated DPAA release coupled with Fe(III) reduction in sulfide environments. The total DPAA fraction decreased significantly to 24.5% after two weeks and reached 3.4% after eight weeks in sulfide soil, whereas no obvious elimination of DPAA occurred in anoxic soil at the initial two weeks and the total DPAA fraction decreased to 10.9% after eight weeks. This can be explained in part by the enhanced mobilization of DPAA and sulfate reduction in sulfide soil compared with anoxic soil. These results suggest that under flooded soil conditions, Fe(III) and sulfate reduction significantly promote DPAA mobilization and thionation, respectively, and we suggest that it is essential to consider both sulfate and Fe(III) reduction to further our understanding of the environmental fate of DPAA.

  8. Effects of buffered vinegar and sodium dodecyl sulfate plus levulinic acid on Salmonella Typhimurium survival, shelf-life, and sensory characteristics of ground beef patties.

    Science.gov (United States)

    Stelzleni, Alexander M; Ponrajan, Amudhan; Harrison, Mark A

    2013-09-01

    The inclusion of two sources of buffered vinegar and sodium dodecyl sulfate plus levulinic acid were studied as interventions for Salmonella Typhimurium and for their effect on shelf-life and sensory characteristics of ground beef. For the Salmonella challenge, beef trimmings (80/20) were inoculated then treated with 2% (w/v) liquid buffered vinegar (LVIN), 2.5% (w/w) powdered buffered vinegar (PVIN), a solution containing 1.0% levulinic acid plus 0.1% sodium dodecyl sulfate (SDLA) at 10% (w/v), or had no intervention applied (CNT). The same trim source and production methods were followed during production of patties for shelf-life and sensory testing without inoculation. SDLA patties had the largest reduction (PSalmonella. However, LVIN and PVIN had the least (Pcharacteristics, except PVIN exhibited stronger off-flavor (P<0.05).

  9. The effect of ammonium sulfate on the solubility of amino acids in water at (298.15 and 323.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Luisa A.; Macedo, Eugenia A. [Laboratory of Separation and Reaction Engineering, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Pinho, Simao P. [Laboratory of Separation and Reaction Engineering, Departamento de Tecnologia Quimica e Biologica, Instituto Politecnico de Braganca, Campus e Santa Apolonia, 5301-857 Braganca (Portugal)], E-mail: spinho@ipb.pt

    2009-02-15

    Using the analytical gravimetric method the solubility of glycine, DL-alanine, L-isoleucine, L-threonine, and L-serine in aqueous systems of (NH{sub 4}){sub 2}SO{sub 4}, at (298.15 and 323.15) K, were measured for salt concentrations ranging up to 2.0 molal. In the electrolyte molality range studied the experimental observations showed that ammonium sulfate is a salting-in agent for most of the amino acids studied. Furthermore, the change of the relative solubility with electrolyte concentration shows a maximum, which makes the representation of the data by a simple empirical correlation such as the Setschenow equation difficult. For the development and evaluation of a robust thermodynamic framework that makes it possible to more profoundly understand aqueous amino acid solutions with ammonium sulfate additional experimental information is needed.

  10. Quantification of phenolic acids and their methylates, glucuronides, sulfates and lactones metabolites in human plasma by LC-MS/MS after oral ingestion of soluble coffee.

    Science.gov (United States)

    Marmet, Cynthia; Actis-Goretta, Lucas; Renouf, Mathieu; Giuffrida, Francesca

    2014-01-01

    Chlorogenic acids and derivatives like phenolic acids are potentially bioactive phenolics, which are commonly found in many foods. Once absorbed, chlorogenic and phenolic acids are highly metabolized by the intestine and the liver, producing glucuronidated and/or sulphated compounds. These metabolites were analyzed in human plasma using a validated liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method. After protein precipitation, phenolic acids and their metabolites were extracted by using ethanol and chromatographic separation was achieved by reversed-phase using an Acquity UPLC BEH C18 column combined with a gradient elution system using 1% acetic acid aqueous solution and 1% acetic acid with 100% acetonitrile. The method was able to quantify 56 different compounds including 24 phenolic acids, 4 lactones, 15 sulfates and 13 glucuronides metabolites between 5 and 1000nM in plasma for most of them, except for m-dihydrocoumaric acid, 5-ferulloylquinic-glucuronide, 4-methoxycinnamic acid, 3-phenylpropionic acid, 3-(4-methoxyphenyl)propionic acid (25 to 1000nM) and p-dihydrocoumaric acid (50-1000nM). Values of repeatability and intermediate reproducibility were below 15% of deviation in general, and maximum 20% for the lowest concentrations. The validated method was successfully applied to quantify phenolic acids and their metabolites in plasma obtained after oral ingestion of soluble coffee. In conclusion, the developed and validated method is proved to be very sensitive, accurate and precise for the quantification of these possible dietary phenols.

  11. Aerosol Chemistry Resolved by Mass Spectrometry: Linking Field Measurements of Cloud Condensation Nuclei Activity to Organic Aerosol Composition.

    Science.gov (United States)

    Vogel, Alexander L; Schneider, Johannes; Müller-Tautges, Christina; Phillips, Gavin J; Pöhlker, Mira L; Rose, Diana; Zuth, Christoph; Makkonen, Ulla; Hakola, Hannele; Crowley, John N; Andreae, Meinrat O; Pöschl, Ulrich; Hoffmann, Thorsten

    2016-10-06

    Aerosol hygroscopic properties were linked to its chemical composition by using complementary online mass spectrometric techniques in a comprehensive chemical characterization study at a rural mountaintop station in central Germany in August 2012. In particular, atmospheric pressure chemical ionization mass spectrometry ((-)APCI-MS) provided measurements of organic acids, organosulfates, and nitrooxy-organosulfates in the particle phase at 1 min time resolution. Offline analysis of filter samples enabled us to determine the molecular composition of signals appearing in the online (-)APCI-MS spectra. Aerosol mass spectrometry (AMS) provided quantitative measurements of total submicrometer organics, nitrate, sulfate, and ammonium. Inorganic sulfate measurements were achieved by semionline ion chromatography and were compared to the AMS total sulfate mass. We found that up to 40% of the total sulfate mass fraction can be covalently bonded to organic molecules. This finding is supported by both on- and offline soft ionization techniques, which confirmed the presence of several organosulfates and nitrooxy-organosulfates in the particle phase. The chemical composition analysis was compared to hy