WorldWideScience

Sample records for acidic sulfate aerosols

  1. Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

    Science.gov (United States)

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

  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 deposition from stratospheric geoengineering with sulfate aerosols

    KAUST Repository

    Kravitz, Ben; Robock, Alan; Oman, Luke; Stenchikov, Georgiy L.; Marquardt, Allison B.

    2009-01-01

    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.

  4. Relative importance of nitrate and sulfate aerosol production mechanisms in urban atmospheres

    International Nuclear Information System (INIS)

    Middleton, P.; Kiang, C.S.

    1979-01-01

    The relative importance of the various sulfate and nitrate aerosol production mechanisms is calculated for different atmospheric conditions. The calculation scheme used to determine the rates of nitrate and sulfate production, based on the concept that vapor transfer to the aerosols and nitrate and sulfate formation within the aerosols are coupled kinetic processes, considers sulfate formation by ozone and hydrogen peroxide oxidation and catalytic oxidation in the presence of soot, iron and manganese of sulfite solutions and sulfuric acid condensation and nitrate formation by the liquid-phase oxidation of dissolved nitrogen oxides for different initial gas concentrations and particle compositions and sizes. It is found that sulfate production is higher under daytime conditions, primarily proceeding by mechanisms involving sulfuric acid and hydrogen peroxide, while at night oxidation processes on the surface of the aerosol film are more important. Nitrate tends to decrease nighttime sulfate production due to an increase in aerosol acidity and nitrate production is found to be higher under nighttime conditions and in the winter

  5. 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

    1997-12-31

    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

  6. 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

  7. Aerosol pH buffering in the southeastern US: Fine particles remain highly acidic despite large reductions in sulfate

    Science.gov (United States)

    Weber, R. J.; Guo, H.; Russell, A. G.; Nenes, A.

    2015-12-01

    pH is a critical aerosol property that impacts many atmospheric processes, including biogenic secondary organic aerosol formation, gas-particle phase partitioning, and mineral dust or redox metal mobilization. Particle pH has also been linked to adverse health effects. Using a comprehensive data set from the Southern Oxidant and Aerosol Study (SOAS) as the basis for thermodynamic modeling, we have shown that particles are currently highly acidic in the southeastern US, with pH between 0 and 2. Sulfate and ammonium are the main acid-base components that determine particle pH in this region, however they have different sources and their concentrations are changing. Over 15 years of network data show that sulfur dioxide emission reductions have resulted in a roughly 70 percent decrease in sulfate, whereas ammonia emissions, mainly link to agricultural activities, have been largely steady, as have gas phase ammonia concentrations. This has led to the view that particles are becoming more neutralized. However, sensitivity analysis, based on thermodynamic modeling, to changing sulfate concentrations indicates that particles have remained highly acidic over the past decade, despite the large reductions in sulfate. Furthermore, anticipated continued reductions of sulfate and relatively constant ammonia emissions into the future will not significantly change particle pH until sulfate drops to clean continental background levels. The result reshapes our expectation of future particle pH and implies that atmospheric processes and adverse health effects linked to particle acidity will remain unchanged for some time into the future.

  8. Cloud albedo changes in response to anthropogenic sulfate and non-sulfate aerosol forcings in CMIP5 models

    Directory of Open Access Journals (Sweden)

    L. Frey

    2017-07-01

    Full Text Available The effects of different aerosol types on cloud albedo are analysed using the linear relation between total albedo and cloud fraction found on a monthly mean scale in regions of subtropical marine stratocumulus clouds and the influence of simulated aerosol variations on this relation. Model experiments from the Coupled Model Intercomparison Project phase 5 (CMIP5 are used to separately study the responses to increases in sulfate, non-sulfate and all anthropogenic aerosols. A cloud brightening on the month-to-month scale due to variability in the background aerosol is found to dominate even in the cases where anthropogenic aerosols are added. The aerosol composition is of importance for this cloud brightening, that is thereby region dependent. There is indication that absorbing aerosols to some extent counteract the cloud brightening but scene darkening with increasing aerosol burden is generally not supported, even in regions where absorbing aerosols dominate. Month-to-month cloud albedo variability also confirms the importance of liquid water content for cloud albedo. Regional, monthly mean cloud albedo is found to increase with the addition of anthropogenic aerosols and more so with sulfate than non-sulfate. Changes in cloud albedo between experiments are related to changes in cloud water content as well as droplet size distribution changes, so that models with large increases in liquid water path and/or cloud droplet number show large cloud albedo increases with increasing aerosol. However, no clear relation between model sensitivities to aerosol variations on the month-to-month scale and changes in cloud albedo due to changed aerosol burden is found.

  9. Secondary sulfate is internally mixed with sea spray aerosol and organic aerosol in the winter Arctic

    Science.gov (United States)

    Kirpes, Rachel M.; Bondy, Amy L.; Bonanno, Daniel; Moffet, Ryan C.; Wang, Bingbing; Laskin, Alexander; Ault, Andrew P.; Pratt, Kerri A.

    2018-03-01

    Few measurements of aerosol chemical composition have been made during the winter-spring transition (following polar sunrise) to constrain Arctic aerosol-cloud-climate feedbacks. Herein, we report the first measurements of individual particle chemical composition near Utqiaġvik (Barrow), Alaska, in winter (seven sample days in January and February 2014). Individual particles were analyzed by computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM-EDX, 24 847 particles), Raman microspectroscopy (300 particles), and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS, 290 particles). Sea spray aerosol (SSA) was observed in all samples, with fresh and aged SSA comprising 99 %, by number, of 2.5-7.5 µm diameter particles, 65-95 % from 0.5-2.5 µm, and 50-60 % from 0.1-0.5 µm, indicating SSA is the dominant contributor to accumulation and coarse-mode aerosol during the winter. The aged SSA particles were characterized by reduced chlorine content with 94 %, by number, internally mixed with secondary sulfate (39 %, by number, internally mixed with both nitrate and sulfate), indicative of multiphase aging reactions during transport. There was a large number fraction (40 % of 1.0-4.0 µm diameter particles) of aged SSA during periods when particles were transported from near Prudhoe Bay, consistent with pollutant emissions from the oil fields participating in atmospheric processing of aerosol particles. Organic carbon and sulfate particles were observed in all samples and comprised 40-50 %, by number, of 0.1-0.4 µm diameter particles, indicative of Arctic haze influence. Soot was internally mixed with organic and sulfate components. All sulfate was mixed with organic carbon or SSA particles. Therefore, aerosol sources in the Alaskan Arctic and resulting aerosol chemical mixing states need to be considered when predicting aerosol climate effects, particularly cloud

  10. Biogenic, anthropogenic and sea salt sulfate size-segregated aerosols in the Arctic summer

    Directory of Open Access Journals (Sweden)

    R. Ghahremaninezhad

    2016-04-01

    Full Text Available Size-segregated aerosol sulfate concentrations were measured on board the Canadian Coast Guard Ship (CCGS Amundsen in the Arctic during July 2014. The objective of this study was to utilize the isotopic composition of sulfate to address the contribution of anthropogenic and biogenic sources of aerosols to the growth of the different aerosol size fractions in the Arctic atmosphere. Non-sea-salt sulfate is divided into biogenic and anthropogenic sulfate using stable isotope apportionment techniques. A considerable amount of the average sulfate concentration in the fine aerosols with a diameter  <  0.49 µm was from biogenic sources (>  63 %, which is higher than in previous Arctic studies measuring above the ocean during fall (<  15 % (Rempillo et al., 2011 and total aerosol sulfate at higher latitudes at Alert in summer (>  30 % (Norman et al., 1999. The anthropogenic sulfate concentration was less than that of biogenic sulfate, with potential sources being long-range transport and, more locally, the Amundsen's emissions. Despite attempts to minimize the influence of ship stack emissions, evidence from larger-sized particles demonstrates a contribution from local pollution. A comparison of δ34S values for SO2 and fine aerosols was used to show that gas-to-particle conversion likely occurred during most sampling periods. δ34S values for SO2 and fine aerosols were similar, suggesting the same source for SO2 and aerosol sulfate, except for two samples with a relatively high anthropogenic fraction in particles  <  0.49 µm in diameter (15–17 and 17–19 July. The high biogenic fraction of sulfate fine aerosol and similar isotope ratio values of these particles and SO2 emphasize the role of marine organisms (e.g., phytoplankton, algae, bacteria in the formation of fine particles above the Arctic Ocean during the productive summer months.

  11. Sulfate Formation on Mars by Volcanic Aerosols: A New Look

    Science.gov (United States)

    Blaney, D. L.

    1996-03-01

    Sulfur was measured at both Viking Lander sites in abundances of 5-9 wt % SO3. Because the sulfur was more concentrated in clumps which disintegrated and the general oxidized nature of the Martian soil, these measurements led to the assumption that a sulfate duricrust existed. Two types of models for sulfate formation have been proposed. One is a formation by upwardly migrating ground water. The other is the formation of sulfates by the precipitation of volcanic aerosols. Most investigators have tended to favor the ground water origin of sulfates on Mars. However, evidence assemble since Viking may point to a volcanic aerosol origin.

  12. 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

    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......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......-limiting step may be the oxidation of sulfite to sulfate, rather than the oxidation of SO2 to SO3 proposed previously. Even though the proposed model is consistent with experimental observations, experiments in a rigorously homogeneous system are called for to test its validity....

  13. Global source attribution of sulfate aerosol and its radiative forcing

    Science.gov (United States)

    Yang, Y.; Wang, H.; Smith, S.; Easter, R. C.; Ma, P. L.; Qian, Y.; Li, C.; Yu, H.; Rasch, P. J.

    2017-12-01

    Sulfate is an important aerosol that poses health risks and influences climate. Due to long-range atmospheric transport, local sulfate pollution could result from intercontinental influences, making domestic efforts of improving air quality inefficient. Accurate understanding of source attribution of sulfate and its radiative forcing is important for both regional air quality improvement and global climate mitigation. In this study, for the first time, a sulfur source-tagging capability is implemented in the Community Atmosphere Model (CAM5) to quantify the global source-receptor relationships of sulfate and its direct and indirect radiative forcing (DRF and IRF). Near-surface sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate is primarily attributed to non-local sources from long-range transport. The export of SO2 and sulfate from Europe contributes 20% of sulfate concentrations over North Africa, Russia and Central Asia. Sources from the Middle East account for 20% of sulfate over North Africa, Southern Africa and Central Asia in winter and autumn, and 20% over South Asia in spring. East Asia accounts for about 50% of sulfate over Southeast Asia in winter and autumn, 15% over Russia in summer, and 10% over North America in spring. South Asia contributes to 25% of sulfate over Southeast Asia in spring. Lifetime of aerosols, together with regional export, is found to determine regional air quality. The simulated global total sulfate DRF is -0.42 W m-2, with 75% contributed by anthropogenic sulfate and 25% contributed by natural sulfate. In the Southern Hemisphere tropics, dimethyl sulfide (DMS) contributes the most to the total DRF. East Asia has the largest contribution of 20-30% over the Northern Hemisphere mid- and high-latitudes. A 20% perturbation of sulfate and its precursor emissions gives a sulfate IRF of -0.44 W m-2. DMS has the

  14. Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

    Science.gov (United States)

    Lei, Ting; Zuend, Andreas; Cheng, Yafang; Su, Hang; Wang, Weigang; Ge, Maofa

    2018-01-01

    Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ˜ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii-Stokes-Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid-liquid equilibrium) in the AIOMFAC and E-AIM models leads to a

  15. Impact of palmitic acid coating on the water uptake and loss of ammonium sulfate particles

    Directory of Open Access Journals (Sweden)

    R. M. Garland

    2005-01-01

    Full Text Available While water insoluble organics are prevalent in the atmosphere, it is not clear how the presence of such species alters the chemical and physical properties of atmospheric aerosols. Here we use a combination of FTIR spectroscopy, Transmission Electron Microscopy (TEM and Aerosol Mass Spectrometry (AMS to characterize ammonium sulfate particles coated with palmitic acid. Coated aerosols were generated by atomizing pure ammonium sulfate, mixing the particles with a heated flow of nitrogen with palmitic acid vapor, and then flowing the mixture through an in-line oven to create internally mixed particles. The mixing state of the particles was probed using the AMS data and images from the TEM. Both of these probes suggest that the particles were internally mixed. Water uptake by the mixed particles was then probed at 273 K. It was found that for ammonium sulfate containing ~20 wt% palmitic acid the deliquescence relative humidity (DRH was the same as for pure ammonium sulfate (80±3% RH. For particles with ~50 wt% palmitic acid however, the mixed particles began to take up water at relative humidities as low at 69% and continued to slowly take up water to 85% RH without fully deliquescing. In addition to studies of water uptake, water loss was also investigated. Here coatings of up to 50 wt% had no impact on the efflorescence relative humidity. These studies suggest that even if insoluble substances coat salt particles in the atmosphere, there may be relatively little effect on the resulting water uptake and loss.

  16. Geo-Engineering Climate Change with Sulfate Aerosol

    Science.gov (United States)

    Rasch, P. J.; Crutzen, P. J.

    2006-12-01

    We explore the impact of injecting a precursor of sulfate aerosols into the middle atmosphere where they would act to increase the planetary albedo and thus counter some of the effects of greenhouse gase forcing. We use an atmospheric general circulation model (CAM, the Community Atmosphere Model) coupled to a slab ocean model for this study. Only physical effects are examined, that is we ignore the biogeochemical and chemical implications of changes to greenhouse gases and aerosols, and do not explore the important ethical, legal, and moral issues that are associated with deliberate geo-engineering efforts. The simulations suggest that the sulfate aerosol produced from the SO2 source in the stratosphere is sufficient to counterbalance most of the warming associated with the greenhouse gas forcing. Surface temperatures return to within a few tenths of a degree(K) of present day levels. Sea ice and precipitation distributions are also much closer to their present day values. The polar region surface temperatures remain 1-3 degrees warm in the winter hemisphere than present day values. This study is very preliminary. Only a subset of the relevant effects have been explored. The effect of such an injection of aerosols on middle atmospheric chemistry, and the effect on cirrus clouds are obvious missing components that merit scrutiny. There are probably others that should be considered. The injection of such aerosols cannot help in ameliorating the effects of CO2 changes on ocean PH, or other effects on the biogeochemistry of the earth system.

  17. Sulfates, Clouds and Radiation Brazil (SCAR-B) AERONET (AErosol RObotic NETwork) Data

    Data.gov (United States)

    National Aeronautics and Space Administration — SCAR_B_AERONET data are Smoke, Clouds and Radiation Brazil (SCARB) Aerosol Robotic Network (AERONET) data for aerosol characterization.Smoke/Sulfates, Clouds and...

  18. Changing transport processes in the stratosphere by radiative heating of sulfate aerosols

    Directory of Open Access Journals (Sweden)

    U. Niemeier

    2017-12-01

    Full Text Available The injection of sulfur dioxide (SO2 into the stratosphere to form an artificial stratospheric aerosol layer is discussed as an option for solar radiation management. Sulfate aerosol scatters solar radiation and absorbs infrared radiation, which warms the stratospheric sulfur layer. Simulations with the general circulation model ECHAM5-HAM, including aerosol microphysics, show consequences of this warming, including changes of the quasi-biennial oscillation (QBO in the tropics. The QBO slows down after an injection of 4 Tg(S yr−1 and completely shuts down after an injection of 8 Tg(S yr−1. Transport of species in the tropics and sub-tropics depends on the phase of the QBO. Consequently, the heated aerosol layer not only impacts the oscillation of the QBO but also the meridional transport of the sulfate aerosols. The stronger the injection, the stronger the heating and the simulated impact on the QBO and equatorial wind systems. With increasing injection rate the velocity of the equatorial jet streams increases, and the less sulfate is transported out of the tropics. This reduces the global distribution of sulfate and decreases the radiative forcing efficiency of the aerosol layer by 10 to 14 % compared to simulations with low vertical resolution and without generated QBO. Increasing the height of the injection increases the radiative forcing only for injection rates below 10 Tg(S yr−1 (8–18 %, a much smaller value than the 50 % calculated previously. Stronger injection rates at higher levels even result in smaller forcing than the injections at lower levels.

  19. Acid aerosol measurement method intercomparisons: An outdoor smog chamber study

    International Nuclear Information System (INIS)

    Ellestad, T.G.; Barnes, H.M.; Kamens, R.M.; McDow, S.R.; Sickles, J.E. II; Hodson, L.L.; Waldman, J.M.; Randtke, S.J.; Lane, D.D.; Springston, S.R.; Koutrakis, P.; Thurston, G.D.

    1991-01-01

    A workshop on the measurement of acid aerosols indicated that the sampling methods in use had not been intercompared. Following two laboratory pilot studies, EPA sponsored tests in an outdoor smog chamber with a variety of test aerosols, including sulfuric acid only, photochemical smog with added sulfuric acid, photo-chemical smog with added sulfuric acid and dust, and dust followed by photochemical smog with added sulfuric acid. Two experiments of each type were conducted. Six groups, several of which were active in ambient acid aerosol measurements, participated by operating duplicate samplers for each experiment. Five groups employed a similar method, in which ammonia is removed from the sample stream by diffusion, particles are removed by Teflon filter, and hydrogen ion on the Teflon filter is determined by pH electrode. However, differences existed in the method's implementation among groups in physical design, flow rate, procedures, and analysis. The sixth group's method did not use a diffusion denuder for ammonia and had several other important differences. Besides hydrogen ion, seven other species were reported by most of the groups, including particle phase sulfate, ammonium, and nitrate, and gas phase sulfur dioxide, ammonia, nitric acid, and nitrous acid. Results of the inter-comparison will be presented

  20. 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.

  1. Extended observations of volcanic SO2 and sulfate aerosol in the stratosphere

    NARCIS (Netherlands)

    Carn, S.A.; Krotkov, N.A.; Yang, Kai; Hoff, R.M.; Prata, A.J.; Krueger, A.J.; Loughlin, S.C.; Levelt, P.F.

    2007-01-01

    Sulfate aerosol produced after injection of sulfur dioxide (SO2) into the stratosphere by volcanic eruptions can trigger climate change. We present new satellite data from the Ozone Monitoring Instrument (OMI) and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) missions

  2. Sulfate metabolism. I. Sulfate uptake and redistribution of acid rain sulfate by edible plants

    International Nuclear Information System (INIS)

    Dallam, R.D.

    1987-01-01

    Sulfur is the major component of polluted air in industrialized societies. Atmospheric sulfur is converted to sulfuric acid through a series of chemical reactions which can eventually reenter many ecosystems. When edible plants are grown in soils containing varying amounts of sulfate, the roots take up and transport inorganic sulfate to the stems and leaves. The sulfate taken up by the roots and the amount transported to the stem and leaves was found to be a function of the concentration of sulfate in the soil. Inorganic sulfate taken up by a corn plant seedling can be rapidly converted to organic sulfate by the root system. Nine days after one of a pair of pea plants was inoculated with artificial acid rain sulfate (dilute H 2 35 SO 4 ) it was found that the sulfate was translocated not only in the inoculated plant, but also to the uninoculated pea plant in the same container. Also, when the leaves of a mature potato plant were inoculated with artificial acid rain sulfate it was found that the sulfate was translocated into the edible potatoes. Fractionation of the potatoes showed that most of the sulfate was water soluble of which 30% was inorganic sulfate and 70% was in the form of organic sulfur. One third of the non-water soluble translocated acid rain sulfate was equally divided between lipid and non-lipid organic sulfur of the potato. 9 references, 2 figures, 5 tables

  3. Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

    Science.gov (United States)

    Wang, Xiaowei; Jing, Bo; Tan, Fang; Ma, Jiabi; Zhang, Yunhong; Ge, Maofa

    2017-10-01

    Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA) and mixed particles composed of ammonium sulfate (AS) and OA with different organic to inorganic molar ratios (OIRs) have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH), and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH) for mixed OA / AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH) of AS in mixed OA / AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA / AS droplets indicate the formation of ammonium hydrogen oxalate (NH4HC2O4) and ammonium hydrogen sulfate (NH4HSO4) from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA / AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH4)2SO4 into NH4HC2O4 with a high DRH. Although the hygroscopic growth of mixed OA / AS droplets is comparable to that of AS or OA at high RH during the dehydration process, Raman growth

  4. On numerical simulation of the global distribution of sulfate aerosol produced by a large volcanic eruption

    Energy Technology Data Exchange (ETDEWEB)

    Pudykiewicz, J.A.; Dastoor, A.P. [Atmospheric Environment Service, Quebec (Canada)

    1994-12-31

    Volcanic eruptions play an important role in the global sulfur cycle of the Earth`s atmosphere and can significantly perturb the global atmospheric chemistry. The large amount of sulfate aerosol produced by the oxidation of SO{sub 2} injected into the atmosphere during volcanic eruptions also has a relatively big influence on the radiative equilibrium of the Earth`s climatic system. The submicron particles of the sulfate aerosol reflect solar radiation more effectively than they trap radiation in the infrared range. The effect of this is observed as cooling of the Earth`s surface. The modification of the global radiation budget following volcanic eruption can subsequently cause significant fluctuations of atmospheric variables on a subclimatic scale. The resulting perturbation of weather patterns has been observed and well documented since the eruptions of Mt. Krakatau and Mt. Tambora. The impact of the sulfate aerosol from volcanic eruptions on the radiative equilibrium of the Earth`s atmosphere was also confirmed by the studies done with Global Circulation Models designed to simulate climate. The objective of the present paper is to present a simple and effective method to estimate the global distribution of the sulfate aerosol produced as a consequence of volcanic eruptions. In this study we will present results of the simulation of global distribution of sulfate aerosol from the eruption of Mt Pinatubo.

  5. Volcanic Plume Impact on the Atmosphere and Climate: O- and S-Isotope Insight into Sulfate Aerosol Formation

    Directory of Open Access Journals (Sweden)

    Erwan Martin

    2018-05-01

    Full Text Available The impact of volcanic eruptions on the climate has been studied over the last decades and the role played by sulfate aerosols appears to be major. S-bearing volcanic gases are oxidized in the atmosphere into sulfate aerosols that disturb the radiative balance on earth at regional to global scales. This paper discusses the use of the oxygen and sulfur multi-isotope systematics on volcanic sulfates to understand their formation and fate in more or less diluted volcanic plumes. The study of volcanic aerosols collected from air sampling and ash deposits at different distances from the volcanic systems (from volcanic vents to the Earth poles is discussed. It appears possible to distinguish between the different S-bearing oxidation pathways to generate volcanic sulfate aerosols whether the oxidation occurs in magmatic, tropospheric, or stratospheric conditions. This multi-isotopic approach represents an additional constraint on atmospheric and climatic models and it shows how sulfates from volcanic deposits could represent a large and under-exploited archive that, over time, have recorded atmospheric conditions on human to geological timescales.

  6. 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

  7. Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase.

    Science.gov (United States)

    Hung, Hui-Ming; Hoffmann, Michael R

    2015-12-01

    The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ≤ 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world.

  8. Impacts of East Asian Sulfate Aerosols on Local and Remote Climate

    Science.gov (United States)

    Bartlett, R. E.; Bollasina, M. A.

    2017-12-01

    Anthropogenic aerosols exert significant climate forcing, which increases with emissions following trends of growing population and industry. Globally, aerosols cause a net cooling, counteracting greenhouse gas warming; however, regional impacts vary since emissions are spatially and temporally heterogeneous. While European and North American emissions have decreased in recent decades, Asian, particularly East Asian, emissions continued to rise into the 21st century. In addition to links between Asian anthropogenic aerosols and significant local climate impacts - for example, changes to the Asian monsoon system - studies have also shown influences on remote climate. Sulfate aerosols are particularly important for East Asia, remaining at constant levels higher than column burdens of other aerosol species. If a concerted effort - as laid out by government policies aiming to improve air quality - is made, the effects of anthropogenic aerosols (due to their short atmospheric lifetime) could be quickly reversed. Thus, it is vital to understand the climate impact aerosols have had up to now to aid in determining what will happen in the future. We use transient climate modelling experiments with the Community Earth System Model to investigate the impacts of East Asian sulfate aerosols in the present day compared to 1950 (i.e. before rapid industrialisation in this region), focusing on dynamical mechanisms leading to the occurrence of such impacts, and how their influence can spread to remote regions. We find, in addition to significant monsoon impacts, noticeable shifts in large-scale circulation features such as the ITCZ and the Pacific Walker cell. Through diabatic heating responses, changes to upper-level atmospheric dynamics are evident, leading to downstream effects on surface climate - for example, surface cooling over Europe. Understanding of these impacts is vital when considering how the good intentions of air quality improvement might inadvertently have

  9. 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.

  10. Sulfation in lead-acid batteries

    Science.gov (United States)

    Catherino, Henry A.; Feres, Fred F.; Trinidad, Francisco

    Virtually, all military land vehicle systems use a lead-acid battery to initiate an engine start. The maintainability of these batteries and as a consequence, system readiness, has suffered from a lack of understanding of the reasons for battery failure. Often, the term most commonly heard for explaining the performance degradation of lead-acid batteries is the word, sulfation. Sulfation is a residual term that came into existence during the early days of lead-acid battery development. The usage is part of the legend that persists as a means for interpreting and justifying the eventual performance deterioration and failure of lead-acid batteries. The usage of this term is confined to the greater user community and, over time, has encouraged a myriad of remedies for solving sulfation problems. One can avoid the connotations associated with the all-inclusive word, sulfation by visualizing the general "sulfation" effect in terms of specific mechanistic models. Also, the mechanistic models are essential for properly understanding the operation and making proper use this battery system. It is evident that the better the model, the better the level of understanding.

  11. Acid Sulfate Alteration on Mars

    Science.gov (United States)

    Ming, D. W.; Morris, R. V.

    2016-01-01

    A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the

  12. Global Distribution of Solid Ammonium Sulfate Aerosols and their Climate Impact Acting as Ice Nuclei

    Science.gov (United States)

    Zhou, C.; Penner, J.

    2017-12-01

    Laboratory experiments show that liquid ammonium sulfate particles effloresce when RHw is below 34% to become solid and dissolve when RHw is above 79%. Solid ammonium sulfate aerosols can act as heterogeneous ice nuclei particles (INPs) to form ice particles in deposition mode when the relative humidity over ice is above 120%. In this study we used the coupled IMPACT/CAM5 model to track the efflorescence and deliquescence processes of ammonium sulfate. Results show that about 20% of the total simulated pure sulfate aerosol mass is in the solid state and is mainly distributed in the northern hemisphere (NH) from 50 hPa to 200 hPa. When these solid ammonium sulfate aerosols are allowed to act as ice nuclei particles, they act to increase the ice water path in the NH and reduce ice water path in the tropics. The addition of these particles leads to a positive net radiative effect at the TOA ranging from 0.5-0.9 W/m2 depending on the amounts of other ice nuclei particles (e.g., dust, soot) used in the ice nucleation process. The short-term climate feedback shows that the ITCZ shifts northwards and precipitation increases in the NH. There is also an average warming of 0.05-0.1 K near the surface (at 2 meter) in the NH which is most obvious in the Arctic region.

  13. Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

    Directory of Open Access Journals (Sweden)

    X. Wang

    2017-10-01

    Full Text Available Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA and mixed particles composed of ammonium sulfate (AS and OA with different organic to inorganic molar ratios (OIRs have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH, and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH for mixed OA ∕ AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH of AS in mixed OA ∕ AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA ∕ AS droplets indicate the formation of ammonium hydrogen oxalate (NH4HC2O4 and ammonium hydrogen sulfate (NH4HSO4 from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA ∕ AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH42SO4 into NH4HC2O4 with a high DRH. Although the hygroscopic growth of mixed OA

  14. Biomass burning and its effects on fine aerosol acidity, water content and nitrogen partitioning

    Science.gov (United States)

    Bougiatioti, Aikaterini; Nenes, Athanasios; Paraskevopoulou, Despina; Fourtziou, Luciana; Stavroulas, Iasonas; Liakakou, Eleni; Myriokefalitakis, Stelios; Daskalakis, Nikos; Weber, Rodney; Kanakidou, Maria; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

    2017-04-01

    Finokalia, Crete. During cleaner days submicron aerosol was found to be more acidic, regardless of the season (winter or summer). This reduced acidity is attributed to the presence of non-volatile cations, such as non-sea salt potassium and the significant excess of ammonium compared to sulfates. The lower pH values leads to the partitioning of the majority of nitrate and chloride to the aerosol phase, which can explain the good correlation found in biomass burning influenced environments between BB tracers and both these species. Finally, we show that these acidity effects of biomass burning can be also seen in regional and global scales, which can have important implications for public health, climate and ecosystems.

  15. Aerosol Chemical Composition and its Effects on Cloud-Aerosol Interactions during the 2007 CHAPS Experiment

    Science.gov (United States)

    Lee, Y.; Alexander, L.; Newburn, M.; Jayne, J.; Hubbe, J.; Springston, S.; Senum, G.; Andrews, B.; Ogren, J.; Kleinman, L.; Daum, P.; Berg, L.; Berkowitz, C.

    2007-12-01

    Chemical composition of submicron aerosol particles was determined using an Aerodyne Time-of-Flight Aerosol Mass Spectrometer (AMS) outfitted on the DOE G-1 aircraft during the Cumulus Humilis Aerosol Processing Study (CHAPS) conducted in Oklahoma City area in June 2007. The primary objective of CHAPS was to investigate the effects of urban emissions on cloud aerosol interactions as a function of processing of the emissions. Aerosol composition was typically determined at three different altitudes: below, in, and above cloud, in both upwind and downwind regions of the urban area. Aerosols were sampled from an isokinetic inlet with an upper size cut-off of ~1.5 micrometer. During cloud passages, the AMS also sampled particles that were dried from cloud droplets collected using a counter-flow virtual impactor (CVI) sampler. The aerosol mass concentrations were typically below 10 microgram per cubic meter, and were dominated by organics and sulfate. Ammonium was often less than required for complete neutralization of sulfate. Aerosol nitrate levels were very low. We noted that nitrate levels were significantly enhanced in cloud droplets compared to aerosols, most likely resulting from dissolution of gaseous nitric acid. Organic to sulfate ratios appeared to be lower in cloud droplets than in aerosols, suggesting cloud condensation nuclei properties of aerosol particles might be affected by loading and nature of the organic components in aerosols. In-cloud formation of sulfate was considered unimportant because of the very low SO2 concentration in the region. A detailed examination of the sources of the aerosol organic components (based on hydrocarbons determined using a proton transfer reaction mass spectrometer) and their effects on cloud formation as a function of atmospheric processing (based on the degree of oxidation of the organic components) will be presented.

  16. 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. © 2013 The Authors Journal compilation © 2013 FEBS.

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

    International Nuclear Information System (INIS)

    Liu Junfeng; Mauzerall, Denise L

    2007-01-01

    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 SO 2 emissions from a source region. We find that due to the non-linear nature of sulfate production, regions with low SO 2 emissions usually have large domestic IP, and vice versa. An exception is East Asia (EA), which has both high SO 2 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. SO 2 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 SO 2 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 SO 2 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

  18. Evaluation of sulfate aerosol optical depths over the North Atlantic and comparison with satellite observations

    International Nuclear Information System (INIS)

    Berkowitz, C.M.; Ghan, S.J.; Benkovitz, C.M.; Wagener, R.; Nemesure, S.; Schwartz, S.E.

    1993-11-01

    It has been postulated that scattering of sunlight by aerosols can significantly reduce the amount of solar energy absorbed by the climate system. Aerosol measurement programs alone cannot provide all the information needed to evaluate the radiative forcing due to anthropogenic aerosols. Thus, comprehensive global-scale aerosol models, properly validated against surface-based and satellite measurements, are a fundamental tool for evaluating the impacts of aerosols on the planetary radiation balance. Analyzed meteorological fields from the European Centre for Medium-Range Weather Forecasts are used to drive a modified version of the PNL Global Chemistry Model, applied to the atmospheric sulfur cycle. The resulting sulfate fields are used to calculate aerosol optical depths, which in turn are compared to estimates of aerosol optical depth based on satellite observations

  19. Investigating the influence of volcanic sulfate aerosol on cloud properties Along A-Train tracks

    Science.gov (United States)

    Mace, G. G.

    2017-12-01

    Marine boundary layer (MBL) clouds are central actors in the climate system given their extensive coverage on the Earth's surface, their 1-way influence on the radiative balance (cooling), and their intimate coupling between air motions, anthropogenic and natural aerosol sources, and processes within the upper ocean mixed layer. Knowledge of how MBL shallow cumulus clouds respond to changes in aerosol is central to understanding how MBL clouds modulate the climate system. A frequent approach to investigating how sulfate aerosol influences MBL clouds has been to examine sulfate plumes extending downstream of active island volcanoes. This approach is challenging due to modification of the air motions in the plumes downstream of islands and due to the tendency of most researchers to examine only level-2 retrievals ignoring the actual data collected by sensors such as MODIS. Past studies have concluded that sulfate aerosols have large effects consistent with the 1st aerosol indirect effect (AIE). We reason that if such effects are as large as suggested in level-2 retrievals then evidence should also be present in the raw MODIS reflectance data as well as other data sources. In this paper we will build on our recently published work where we tested that hypothesis from data collected near Mount Kilauea during a 3-year period. Separating data into aerosol optical depth (A) quartiles, we found little support for a large 1st AIE response. We did find an unambiguous increase in sub 1km-scale cloud fraction with A. This increase in sub 1 km cloud fraction was entirely consistent with increased reflectance with increasing A that is used, via the level 2 retrievals, to argue for a large AIE response of MBL clouds. While the 1-km pixels became unambiguously brighter, that brightening was due to increased sub 1 km cloud fraction and not necessarily due to changes in pixel-level cloud microphysics. We also found that MBL cloud top heights increase as do surface wind speeds as

  20. 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.

  1. Black Carbon and Sulfate Aerosols in the Arctic: Long-term Trends, Radiative Impacts, and Source Attributions

    Science.gov (United States)

    Wang, H.; Zhang, R.; Yang, Y.; Smith, S.; Rasch, P. J.

    2017-12-01

    The Arctic has warmed dramatically in recent decades. As one of the important short-lived climate forcers, aerosols affect the Arctic radiative budget directly by interfering radiation and indirectly by modifying clouds. Light-absorbing particles (e.g., black carbon) in snow/ice can reduce the surface albedo. The direct radiative impact of aerosols on the Arctic climate can be either warming or cooling, depending on their composition and location, which can further alter the poleward heat transport. Anthropogenic emissions, especially, BC and SO2, have changed drastically in low/mid-latitude source regions in the past few decades. Arctic surface observations at some locations show that BC and sulfate aerosols had a decreasing trend in the recent decades. In order to understand the impact of long-term emission changes on aerosols and their radiative effects, we use the Community Earth System Model (CESM) equipped with an explicit BC and sulfur source-tagging technique to quantify the source-receptor relationships and decadal trends of Arctic sulfate and BC and to identify variations in their atmospheric transport pathways from lower latitudes. The simulation was conducted for 36 years (1979-2014) with prescribed sea surface temperatures and sea ice concentrations. To minimize potential biases in modeled large-scale circulations, wind fields in the simulation are nudged toward an atmospheric reanalysis dataset, while atmospheric constituents including water vapor, clouds, and aerosols are allowed to evolve according to the model physics. Both anthropogenic and open fire emissions came from the newly released CMIP6 datasets, which show strong regional trends in BC and SO2 emissions during the simulation time period. Results show that emissions from East Asia and South Asia together have the largest contributions to Arctic sulfate and BC concentrations in the upper troposphere, which have an increasing trend. The strong decrease in emissions from Europe, Russia and

  2. 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

  3. The boiling point of stratospheric aerosols.

    Science.gov (United States)

    Rosen, J. M.

    1971-01-01

    A photoelectric particle counter was used for the measurement of aerosol boiling points. The operational principle involves raising the temperature of the aerosol by vigorously heating a portion of the intake tube. At or above the boiling point, the particles disintegrate rather quickly, and a noticeable effect on the size distribution and concentration is observed. Stratospheric aerosols appear to have the same volatility as a solution of 75% sulfuric acid. Chemical analysis of the aerosols indicates that there are other substances present, but that the sulfate radical is apparently the major constituent.

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

    International Nuclear Information System (INIS)

    Rocha, Angela S.; Costa, Gustavo C.; Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B.

    2017-01-01

    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 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 − surface group was replaced by a HSO 4 − . 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 4 − 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 2 O 5 ) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

  5. Nucleation and growth of sulfate aerosol in coal-fired power plant plumes: sensitivity to background aerosol and meteorology

    Science.gov (United States)

    Stevens, R. G.; Pierce, J. R.; Brock, C. A.; Reed, M. K.; Crawford, J. H.; Holloway, J. S.; Ryerson, T. B.; Huey, L. G.; Nowak, J. B.

    2012-01-01

    New-particle formation in the plumes of coal-fired power plants and other anthropogenic sulfur sources may be an important source of particles in the atmosphere. It remains unclear, however, how best to reproduce this formation in global and regional aerosol models with grid-box lengths that are 10s of kilometers and larger. The predictive power of these models is thus limited by the resultant uncertainties in aerosol size distributions. In this paper, we focus on sub-grid sulfate aerosol processes within coal-fired power plant plumes: the sub-grid oxidation of SO2 with condensation of H2SO4 onto newly-formed and pre-existing particles. We have developed a modeling framework with aerosol microphysics in the System for Atmospheric Modelling (SAM), a Large-Eddy Simulation/Cloud-Resolving Model (LES/CRM). The model is evaluated against aircraft observations of new-particle formation in two different power-plant plumes and reproduces the major features of the observations. We show how the downwind plume aerosols can be greatly modified by both meteorological and background aerosol conditions. In general, new-particle formation and growth is greatly reduced during polluted conditions due to the large pre-existing aerosol surface area for H2SO4 condensation and particle coagulation. The new-particle formation and growth rates are also a strong function of the amount of sunlight and NOx since both control OH concentrations. The results of this study highlight the importance for improved sub-grid particle formation schemes in regional and global aerosol models.

  6. 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.

  7. 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.

  8. Effect of acidic seed on biogenic secondary organic aerosol growth

    Science.gov (United States)

    Czoschke, Nadine M.; Jang, Myoseon; Kamens, Richard M.

    Secondary organic aerosol (SOA) growth in the presence of acid aerosols was studied in twin 500 l Teflon bags and in a 4 m flow reactor. In Teflon bags, isoprene, acrolein and α-pinene were all made to react individually with ozone and exposed to either acid or non-acid inorganic seed aerosols to determine the effect of acid-catalyzed heterogeneous reactions on SOA growth. α-Pinene and ozone were made to react in a flow reactor to assess the immediate effect of mixing an acid aerosol with SOA at high and low relative humidity levels. In all cases, exposure to acid seed aerosol increased the amount of SOA mass produced. Fourier transform infrared spectra of the SOA in acid systems confirmed the transformation of carbonyl functional groups through acid-catalyzed heterogeneous reactions when SOAs formed in acidic environments or were exposed to acidic aerosols. Organic products initially produced from ozonation in the gas phase partition onto the inorganic seed aerosol and react heterogeneously with an acid catalyst forming low vapor pressure products. These acid-catalyzed heterogeneous reactions are implicated in generating the increased SOA mass observed in acidic aerosol systems as they transform predominantly gas phase compounds of high volatility into low vapor pressure predominantly particle phase products.

  9. Antarctic aerosols - A review

    Science.gov (United States)

    Shaw, Glenn E.

    1988-02-01

    Tropospheric aerosols with the diameter range of half a micron reside in the atmosphere for tens of days and teleconnect Antarctica with other regions by transport that reaches planetary scales of distances; thus, the aerosol on the Antarctic ice represents 'memory modules' of events that took place at regions separated from Antarctica by tens of thousands of kilometers. In terms of aerosol mass, the aerosol species include insoluble crustal products (less than 5 percent), transported sea-salt residues (highly variable but averaging about 10 percent), Ni-rich meteoric material, and anomalously enriched material with an unknown origin. Most (70-90 percent by mass) of the aerosol over the Antarctic ice shield, however, is the 'natural acid sulfate aerosol', apparently deriving from biological processes taking place in the surrounding oceans.

  10. Acidity characterization of a titanium and sulfate modified vermiculite

    International Nuclear Information System (INIS)

    Hernandez, W.Y.; Centeno, M.A.; Odriozola, J.A.; Moreno, S.; Molina, R.

    2008-01-01

    A natural vermiculite has been modified with titanium and sulfated by the intercalation and impregnation method in order to optimize the acidity of the clay mineral, and characterization of samples were analyzed by X-ray fluorescence (XRF), X-ray diffraction (XRD), nitrogen adsorption isotherms, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature programmed desorption with ammonia (TPD-NH 3 ). All the modified solids have a significantly higher number of acidic sites with respect to the parent material and in all of these, Broensted as well as Lewis acidity are identified. The presence of sulfate appears not to increase the number of acidic centers in the modified clay. For the materials sulfated with the intercalation method, it is observed that the strength of the acidic sites found in the material increases with the nominal sulfate/metal ratio. Nevertheless, when elevated quantities of sulfur are deposited, diffusion problems in the heptane reaction appear

  11. 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...

  12. 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

    Science.gov (United States)

    Harris, E.; Sinha, B.; Hoppe, P.; Foley, S.; Borrmann, S.

    2012-05-01

    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 the alkalinity non

  13. 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

  14. Nucleation and growth of sulfate aerosol in coal-fired power plant plumes: sensitivity to background aerosol and meteorology

    Directory of Open Access Journals (Sweden)

    R. G. Stevens

    2012-01-01

    Full Text Available New-particle formation in the plumes of coal-fired power plants and other anthropogenic sulfur sources may be an important source of particles in the atmosphere. It remains unclear, however, how best to reproduce this formation in global and regional aerosol models with grid-box lengths that are 10s of kilometers and larger. The predictive power of these models is thus limited by the resultant uncertainties in aerosol size distributions. In this paper, we focus on sub-grid sulfate aerosol processes within coal-fired power plant plumes: the sub-grid oxidation of SO2 with condensation of H2SO4 onto newly-formed and pre-existing particles. We have developed a modeling framework with aerosol microphysics in the System for Atmospheric Modelling (SAM, a Large-Eddy Simulation/Cloud-Resolving Model (LES/CRM. The model is evaluated against aircraft observations of new-particle formation in two different power-plant plumes and reproduces the major features of the observations. We show how the downwind plume aerosols can be greatly modified by both meteorological and background aerosol conditions. In general, new-particle formation and growth is greatly reduced during polluted conditions due to the large pre-existing aerosol surface area for H2SO4 condensation and particle coagulation. The new-particle formation and growth rates are also a strong function of the amount of sunlight and NOx since both control OH concentrations. The results of this study highlight the importance for improved sub-grid particle formation schemes in regional and global aerosol models.

  15. Small molecules as tracers in atmospheric secondary organic aerosol

    Science.gov (United States)

    Yu, Ge

    Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

  16. A novel tandem differential mobility analyzer with organic vapor treatment of aerosol particles

    Directory of Open Access Journals (Sweden)

    J. Joutsensaari

    2001-01-01

    Full Text Available A novel method to characterize the organic composition of aerosol particles has been developed. The method is based on organic vapor interaction with aerosol particles and it has been named an Organic Tandem Differential Mobility Analyzer (OTDMA. The OTDMA method has been tested for inorganic (sodium chloride and ammonium sulfate and organic (citric acid and adipic acid particles. Growth curves of the particles have been measured in ethanol vapor and as a comparison in water vapor as a function of saturation ratio. Measurements in water vapor show that sodium chloride and ammonium sulfate as well as citric acid particles grow at water saturation ratios (S of 0.8 and above, whereas adipic acid particles do not grow at S S = 0.75 and S = 0.79, respectively. Citric acid particles grow monotonously with increasing saturation ratios already at low saturation ratios and no clear deliquescence point is found. For sodium chloride and ammonium sulfate particles, no growth can be seen in ethanol vapor at saturation ratios below 0.93. In contrast, for adipic acid particles, the deliquescence takes place at around S = 0.95 in the ethanol vapor. The recrystallization of adipic acid takes place at S The results show that the working principles of the OTDMA are operational for single-component aerosols. Furthermore, the results indicate that the OTDMA method may prove useful in determining whether aerosol particles contain organic substances, especially if the OTDMA is operated in parallel with a hygroscopicity TDMA, as the growth of many substances is different in ethanol and water vapors.

  17. Investigation of the atmospheric behavior of dicarboxylic acids and other polar organic aerosol constituents

    International Nuclear Information System (INIS)

    Limbeck, A.

    2001-05-01

    The objective of the present work was to improve the present knowledge about the atmospheric behavior of polar organic aerosol constituents with special respect to dicarboxylic acids. To enable the simultaneous determination of polar organic compounds in atmospheric samples like aerosol or precipitation samples (atmospheric hydrometeors) a new GCMS method was developed. Almost all classes of oxygenated organic compounds like mono- and dicarboxylic acids, aldehydes, alcohols or polar aromatic compounds like phthalates could be determined with only one sample preparation scheme. The separation into two classes of organic compounds with different polarity was performed using solid phase extraction. After a sample pre-treatment of the derived fractions, including esterification of the acids and extraction with cyclohexane, the samples were analyzed with a GCMS system. The new method was applied for the analysis of simultaneously collected interstitial aerosol and cloud water samples from a continental background site in Central Europe (Sonnblick Observatory, located at 3106-m elevation in the Austrian Alps). In all samples a large variety of mono- and dicarboxylic acids were identified and quantified, together with some aldehydes, alcohols and aromatic compounds. Using the obtained data set, for the first time in-cloud scavenging efficiencies for dicarboxylic acids, monocarboxylic acids, and other polar organic compounds were calculated. The results were compared to sulfate, which exhibited an average scavenging efficiency of 0.94. In the last part of the present work the results from laboratory and field investigations conducted with the intention to yield an improved sampling technique for the correction of the positive sampling artifact (adsorption of gas phase organics onto the filter substrate) were presented. (author)

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

    OpenAIRE

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

    2013-01-01

    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...

  19. Sub-Antarctic marine aerosol: dominant contributions from biogenic sources

    Directory of Open Access Journals (Sweden)

    J. Schmale

    2013-09-01

    Full Text Available Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS, was 21% non-sea-salt sulfate, 2% nitrate, 8% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea spray signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA profiles could be isolated: an amino acid/amine factor (AA-OA, 18% of OA mass, a methanesulfonic acid OA factor (MSA-OA, 25%, a marine oxygenated OA factor (M-OOA, 41%, a sea spray OA fraction (SS-OA, 7% and locally produced hydrocarbon-like OA (HOA, 9%. The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (N : C ratio = 0.13, has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea spray aerosol was identified (SS-OA. However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not

  20. Organic aerosols

    International Nuclear Information System (INIS)

    Penner, J.E.

    1994-01-01

    Organic aerosols scatter solar radiation. They may also either enhance or decrease concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the sources of organic aerosol matter. The anthropogenic sources of organic aerosols may be as large as the anthropogenic sources of sulfate aerosols, implying a similar magnitude of direct forcing of climate. The source estimates are highly uncertain and subject to revision in the future. A slow secondary source of organic aerosols of unknown origin may contribute to the observed oceanic concentrations. The role of organic aerosols acting as cloud condensation nuclei (CCN) is described and it is concluded that they may either enhance or decrease the ability of anthropogenic sulfate aerosols to act as CCN

  1. 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.

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

    Directory of Open Access Journals (Sweden)

    J.-E. Tesdal

    2016-09-01

    Full Text Available 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.

  3. Formation of aqueous-phase sulfate during the haze period in China: Kinetics and atmospheric implications

    Science.gov (United States)

    Zhang, Haijie; Chen, Shilu; Zhong, Jie; Zhang, Shaowen; Zhang, Yunhong; Zhang, Xiuhui; Li, Zesheng; Zeng, Xiao Cheng

    2018-03-01

    Sulfate is one of the most important components in the aerosol due to its key role in air pollution and global climate change. Recent work has suggested that reactive nitrogen chemistry in aqueous water can explain the missing source of sulfate in the aqueous water. Herein, we have mapped out the energy profile of the oxidization process of SO2 leading from NO2 and two feasible three-step mechanisms have been proposed. For the oxidation of HOSO2- and HSO3- by the dissolved NO2 in weakly acidic and neutral aerosol (pH ≤ 7), the main contribution to the missing sulfate production comes from the oxidation of HOSO2-. The whole process is a self-sustaining process. For the oxidation of SO32- in alkaline aerosol (pH > 7), the third step - decomposition step of H2O or hydrolysis of SO3 step which are two parallel processes are the rate-limiting steps. The present results are of avail to better understand the missing source of sulfate in the aerosol and hence may lead to better science-based solutions for resolving the severe haze problems in China.

  4. Simulated responses of terrestrial aridity to black carbon and sulfate aerosols

    Science.gov (United States)

    Lin, L.; Gettelman, A.; Xu, Y.; Fu, Q.

    2016-01-01

    Aridity index (AI), defined as the ratio of precipitation to potential evapotranspiration (PET), is a measure of the dryness of terrestrial climate. Global climate models generally project future decreases of AI (drying) associated with global warming scenarios driven by increasing greenhouse gas and declining aerosols. Given their different effects in the climate system, scattering and absorbing aerosols may affect AI differently. Here we explore the terrestrial aridity responses to anthropogenic black carbon (BC) and sulfate (SO4) aerosols with Community Earth System Model simulations. Positive BC radiative forcing decreases precipitation averaged over global land at a rate of 0.9%/°C of global mean surface temperature increase (moderate drying), while BC radiative forcing increases PET by 1.0%/°C (also drying). BC leads to a global decrease of 1.9%/°C in AI (drying). SO4 forcing is negative and causes precipitation a decrease at a rate of 6.7%/°C cooling (strong drying). PET also decreases in response to SO4 aerosol cooling by 6.3%/°C cooling (contributing to moistening). Thus, SO4 cooling leads to a small decrease in AI (drying) by 0.4%/°C cooling. Despite the opposite effects on global mean temperature, BC and SO4 both contribute to the twentieth century drying (AI decrease). Sensitivity test indicates that surface temperature and surface available energy changes dominate BC- and SO4-induced PET changes.

  5. Isotopic constraints on heterogeneous sulfate production in Beijing haze

    Science.gov (United States)

    He, Pengzhen; Alexander, Becky; Geng, Lei; Chi, Xiyuan; Fan, Shidong; Zhan, Haicong; Kang, Hui; Zheng, Guangjie; Cheng, Yafang; Su, Hang; Liu, Cheng; Xie, Zhouqing

    2018-04-01

    (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6 ± 0.1 or 4.7 ± 1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO2 and by O2. Our local atmospheric conditions-based calculations suggest sulfate formation via NO2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of Δ17O(SO42-) for quantifying sulfate formation pathways, but this estimate may be further improved with future regional modeling work.

  6. Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

    Directory of Open Access Journals (Sweden)

    E. M. Knipping

    2011-02-01

    Full Text Available The secondary organic aerosol (SOA yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS. A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS.

  7. Pollutants identification of ambient aerosols by two types of aerosol mass spectrometers over southeast coastal area, China.

    Science.gov (United States)

    Yan, Jinpei; Chen, Liqi; Lin, Qi; Zhao, Shuhui; Li, Lei

    2018-02-01

    Two different aerosol mass spectrometers, Aerodyne Aerosol Mass Spectrometer (AMS) and Single Particle Aerosol Mass Spectrometer (SPAMS) were deployed to identify the aerosol pollutants over Xiamen, representing the coastal urban area. Five obvious processes were classified during the whole observation period. Organics and sulfate were the dominant components in ambient aerosols over Xiamen. Most of the particles were in the size range of 0.2-1.0μm, accounting for over 97% of the total particles measured by both instruments. Organics, as well as sulfate, measured by AMS were in good correlation with measured by SPAMS. However, high concentration of NH 4 + was obtained by AMS, while extremely low value of NH 4 + was detected by SPAMS. Contrarily, high particle number counts of NO 3 - and Cl - were given by SPAMS while low concentrations of NO 3 - and Cl - were measured by AMS. The variations of POA and SOA obtained from SPAMS during event 1 and event 2 were in accordance with the analysis of HOA and OOA given by AMS, suggesting that both of AMS and SPAMS can well identify the organic clusters of aerosol particles. Overestimate or underestimate of the aerosol sources and acidity would be present in some circumstances when the measurement results were used to analyze the aerosol properties, because of the detection loss of some species for both instruments. Copyright © 2017. Published by Elsevier B.V.

  8. Processing of Unsaturated Organic Acid Aerosols by Ozone

    Science.gov (United States)

    Aloisio, S.; Donaldson, D. J.; Eliason, T. L.; Cziczo, D.; Vaida, V.

    2002-05-01

    We present results of in-situ studies of the oxidative "processing" of organic aerosols composed of unsaturated organic compounds. Aerosol samples of 2-octenoic acid and undecylenic acid were exposed to approx. 10 mbar ozone in a room temperature, atmospheric pressure flow tube reactor. In-situ spectroscopic probing of the reaction mixture, as well as GC-MS analysis of the flow tube effluent, shows evidence of efficient oxidation of double bonds in the organic species, with production of gas-phase and aerosol phase ozonolysis products.

  9. 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).

  10. Behavior of copper in acidic sulfate solution: Comparison with acidic chloride

    Energy Technology Data Exchange (ETDEWEB)

    Tromans, D.; Silva, J.C. [Univ. of British Columbia, Vancouver, British Columbia (Canada). Dept. of Metals and Materials Engineering

    1997-03-01

    The anodic polarization behavior of copper in a 0.1 M sulfuric acid (H{sub 2}SO{sub 4}) + 1 M sodium sulfate (Na{sub 2}SO{sub 4}) solution (pH = 2.0) was studied at room temperature under quiescent and stirred conditions. The behavior was compared with aqueous equilibria via construction of a potential-vs-pH (E-pH) diagram for the copper-sulfate-water (Cu-SO{sub 4}{sup 2}-H{sub 2}O) system. Interpretation of the behavior was aided by comparison with aqueous equilibria and polarization studies of copper in a 0.2 M hydrochloric acid (HCl) + 1 M sodium chloride (NaCl) solution(pH = 0.8). The initial anodic dissolution region in the acidic sulfate solution exhibited Tafel behavior with a slope consistent with formation of cupric ions (Cu{sup 2+}) whose rate of formation was charge-transfer controlled. At higher potentials, limiting current density (i{sub L}) behavior was observed under E-pH conditions that were consistent with formation of a film of copper sulfate pentahydrate (CuSO{sub 4} {degree} 5H{sub 2}O). Comparison of experimental i{sub L} values with those predicted by mass transport-controlled processes, using estimates of the diffusion layer thickness obtained from the mass transfer-influenced region of apparent Tafel behavior in the acidic chloride solution, were in sufficient agreement to indicate i{sub L} was controlled by the rate of dissolution of the CuSO{sub 4} {degree} 5H{sub 2}O film via transport of Cu{sup 2+} from the film-electrolyte interface into the bulk solution.

  11. 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

    Directory of Open Access Journals (Sweden)

    D. K. Deshmukh

    2016-04-01

    Full Text Available Size-segregated aerosols (nine stages from < 0.43 to > 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.

  12. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    Directory of Open Access Journals (Sweden)

    M. R. Beaver

    2006-01-01

    Full Text Available Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10 and ketones (C3 and C9 on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  13. 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...

  14. Health effects of acid aerosols formed by atmospheric mixtures

    International Nuclear Information System (INIS)

    Kleinman, M.T.; Phalen, R.F.; Mautz, W.J.; Mannix, R.C.; McClure, T.R.; Crocker, T.T.

    1989-01-01

    Under ambient conditions, sulfur and nitrogen oxides can react with photochemical products and airborne particles to form acidic vapors and aerosols. Inhalation toxicological studies were conducted, exposing laboratory animals, at rest and during exercise, to multicomponent atmospheric mixtures under conditions favorable to the formation of acidic reaction products. Effects of acid and ozone mixtures on early and late clearance of insoluble radioactive particles in the lungs of rats appeared to be dominated by the oxidant component (i.e., the mixture did cause effects that were significantly different from those of ozone alone). Histopathological evaluations showed that sulfuric acid particles alone did not cause inflammatory responses in centriacinar units of rat lung parenchyma (expressed in terms of percent lesion area) but did cause significant damage (cell killing followed by a wave of cell replication) in nasal respiratory epithelium, as measured by uptake of tritiated thymidine in the DNA of replicating cells. Mixtures of ozone and nitrogen dioxide, which form nitric acid, caused significant inflammatory responses in lung parenchyma (in excess of effects seen in rats exposed to ozone alone), but did not damage nasal epithelium. Mixtures containing acidic sulfate particles, ozone, and nitrogen dioxide damaged both lung parenchyma and nasal epithelia. In rats exposed at rest, the response of the lung appeared to be dominated by the oxidant gas-phase components, while responses in the nose were dominated by the acidic particles. In rats exposed at exercise, however, mixtures of ozone and sulfuric acid particles significantly (2.5-fold) elevated the degree of lung lesion formation over that seen in rats exposed to ozone alone under an identical exercise protocol

  15. Atmospheric oxidation of isoprene and 1,3-Butadiene: influence of aerosol acidity and Relative humidity on secondary organic aerosol

    Science.gov (United States)

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA)have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air s...

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

    DEFF Research Database (Denmark)

    Beucher, Amélie; Boman, A; Mattbäck, S

    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...... obtained from a EM38 proximal sensor enabled the refined mapping of acid sulfate soils over a field (Huang et al. 2014). The present study aims at developing an efficient and reliable method for the detailed predictive mapping of acid sulfate soil occurrence in a field located in western Finland. Different...

  17. 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.

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

    Science.gov (United States)

    Adachi, K.; Buseck, P. R.

    2008-05-01

    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.

  19. Tropospheric chemistry of natural hydrocarbons, aldehydes, and peroxy radicals: Their connections to sulfuric acid production and climate effects

    International Nuclear Information System (INIS)

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

    1993-05-01

    Recent work has shown that natural hydrocarbon emissions can significantly affect the levels of urban and regional tropospheric ozone. We report on the reactivities of these biogenic trace gases, particularly isoprene, focusing on their importance in the production of aldehydes and peroxy radicals, leading to increased levels of hydrogen over regional forests. Hydrogen peroxide can lead to the wet oxidation of sulfur dioxide to acidic sulfate in aerosols, fogs, and clouds. In turn, acidic sulfate can act to as a light scattering aerosol and a source of cloud condensation nuclei (CCN), potentially leading to global cooling. Aerosol sulfate and other dissolved organic and inorganic compounds can also play important roles as a greenhouse species in the lower troposphere

  20. Isotopic constraints on heterogeneous sulfate production in Beijing haze

    Directory of Open Access Journals (Sweden)

    P. He

    2018-04-01

    radical chain mechanism, contributed the remaining 66–73 % of Phet. The assumption about the thermodynamic state of aerosols (stable or metastable was found to significantly influence the calculated aerosol pH (7.6  ±  0.1 or 4.7  ±  1.1, respectively, and thus influence the relative importance of heterogeneous sulfate production via S(IV oxidation by NO2 and by O2. Our local atmospheric conditions-based calculations suggest sulfate formation via NO2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV oxidation by O2 can be the dominant pathway providing that highly acidic aerosols (pH  ≤  3 exist. Our local atmospheric-conditions-based calculations illustrate the utility of Δ17O(SO42− for quantifying sulfate formation pathways, but this estimate may be further improved with future regional modeling work.

  1. Agglomerated novel spray-dried lactose-leucine tailored as a carrier to enhance the aerosolization performance of salbutamol sulfate from DPI formulations.

    Science.gov (United States)

    Molina, Carlos; Kaialy, Waseem; Chen, Qiao; Commandeur, Daniel; Nokhodchi, Ali

    2017-12-19

    Spray-drying allows to modify the physicochemical/mechanical properties of particles along with their morphology. In the present study, L -leucine with varying concentrations (0.1, 0.5, 1, 5, and 10% w/v) were incorporated into lactose monohydrate solution for spray-drying to enhance the aerosolization performance of dry powder inhalers containing spray-dried lactose-leucine and salbutamol sulfate. The prepared spray-dried lactose-leucine carriers were analyzed using laser diffraction (particle size), differential scanning calorimetry (thermal behavior), scanning electron microscopy (morphology), powder X-ray diffraction (crystallinity), Fourier transform infrared spectroscopy (interaction at molecular level), and in vitro aerosolization performance (deposition). The results showed that the efficacy of salbutamol sulfate's aerosolization performance was, in part, due to the introduction of L -leucine in the carrier, prior to being spray-dried, accounting for an increase in the fine particle fraction (FPF) of salbutamol sulfate from spray-dried lactose-leucine (0.5% leucine) in comparison to all other carriers. It was shown that all of the spray-dried carriers were spherical in their morphology with some agglomerates and contained a mixture of amorphous, α-lactose, and β-lactose. It was also interesting to note that spray-dried lactose-leucine particles were agglomerated during the spray-drying process to make coarse particles (volume mean diameter of 79 to 87 μm) suitable as a carrier in DPI formulations.

  2. 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.

  3. Remote sensing of acid sulfate soils using multispectral and gamma-ray data

    International Nuclear Information System (INIS)

    Bierwirth, P.N.; Graham, T.L.

    1998-01-01

    Acid sulfate soils are a significant environmental problem in coastal regions of Australia. Drainage and disturbance of coastal lands can result in acid soil degradation and the release of sulfuric acid and toxic metals into coastal waters. Remote sensing can provide a useful tool for detection of these soils and monitoring of their disturbance. As acid sulfate soils become oxidised with exposure to air, iron-minerals are produced and precipitate at the surface. This results from the breakdown of pyrite to form hydrated iron minerals and elemental sulfur, the oxidation of which produces acidity. The concentration of iron minerals at the surface can be an indicator of the level of acid sulfate soil activity in the near subsurface. These iron minerals include goethite, ferrihydrite and jarosite. Space-borne remote sensing scanners such as Landsat TM are capable of detecting iron minerals as a result of ferric ion absorption of solar radiation. Hyperspectral scanners are capable of further discrimination of individual minerals. This paper will discuss spectral characteristics of active acid sulfate soils and demonstrate the use of spectral unmixing algorithms on Landsat TM to detect problem areas at the surface. This method matches multispectral data to material reflectance-spectra known as end-members. These end-members or materials are then resolved mathematically as to their respective contributions to the overall reflectance (Bierwirth, 1990). In this way, abundances for particular materials can be derived.Digital elevation data was used to distinguish between the iron minerals due to weathering of bedrock in upland areas and acid sulfate soils on the plains. Also, the results of a high resolution (200m linespacing) airborne gamma-ray survey are presented. This data senses the concentration of radioelements down to about 40 cm depth and is largely unaffected by vegetation. Concentrations of gamma-emitting elements can indicate the type and depth of alluvium that

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

    DEFF Research Database (Denmark)

    Beucher, Amélie; Peng, Yi; Knadel, Maria

    , including geology, landscape type and terrain parameters. Visible-Near-Infrared (Vis-NIR) spectroscopy constitutes a rapid and cheap alternative to soil analysis, and was successfully utilized for the prediction of soil chemical, physical and biological properties. In particular, the Vis-NIR spectra contain......Releasing acidity and metals into watercourses, acid sulfate soils represent a critical environmental problem worldwide. Identifying the spatial distribution of these soils enables to target the strategic areas for risk management. In Denmark, the occurrence of acid sulfate soils was first studied...... during the 1980’s through conventional mapping (i.e. soil sampling and the subsequent determination of pH at the time of sampling and after incubation, the pyrite content and the acid-neutralizing capacity). Since acid sulfate soils mostly occur in wetlands, the survey specifically targeted these areas...

  5. Radiocarbon variability of fatty acids in semi-urban aerosol samples

    International Nuclear Information System (INIS)

    Matsumoto, Kohei; Uchida, Masao; Kawamura, Kimitaka; Shibata, Yasuyuki; Morita, Masatoshi

    2004-01-01

    We analyzed radiocarbon and the stable carbon isotope ratio for individual monocarboxylic (fatty) acids in an aerosol sample (QFF 2138) and compared the results with data of the aerosol sample taken in another year. The fatty acid concentration distribution of aerosol sample QFF 2138 showed a bimodal pattern with maxima at C 16 and C 26 . Stable carbon isotope ratios of the fatty acids ranged from -30.8 per mille to -23.0 per mille which indicates the animal and/or marine algae origins for C 16 -C 19 fatty acids and mainly terrestrial C 3 plant origins for C >20 fatty acids. Δ 14 C values for fatty acids ranged from -89.7 per mille to +83.5 per mille. Compared with QFF1969, we found that the Δ 14 C values of fatty acids exhibited a wide diversity and Δ 14 C values for each fatty acid in QFF 2138 were largely different from those of QFF 1969

  6. Evaluation of simulated aerosol properties with the aerosol-climate model ECHAM5-HAM using observations from the IMPACT field campaign

    Directory of Open Access Journals (Sweden)

    G.-J. Roelofs

    2010-08-01

    Full Text Available In May 2008, the measurement campaign IMPACT for observation of atmospheric aerosol and cloud properties was conducted in Cabauw, The Netherlands. With a nudged version of the coupled aerosol-climate model ECHAM5-HAM we simulate the size distribution and chemical composition of the aerosol and the associated aerosol optical thickness (AOT for the campaign period. Synoptic scale meteorology is represented realistically through nudging of the vorticity, the divergence, the temperature and the surface pressure. Simulated concentrations of aerosol sulfate and organics at the surface are generally within a factor of two from observed values. The monthly averaged AOT from the model is 0.33, about 20% larger than observed. For selected periods of the month with relatively dry and moist conditions discrepancies are approximately −30% and +15%, respectively. Discrepancies during the dry period are partly caused by inaccurate representation of boundary layer (BL dynamics by the model affecting the simulated AOT. The model simulates too strong exchange between the BL and the free troposphere, resulting in weaker concentration gradients at the BL top than observed for aerosol and humidity, while upward mixing from the surface layers into the BL appears to be underestimated. The results indicate that beside aerosol sulfate and organics also aerosol ammonium and nitrate significantly contribute to aerosol water uptake. The simulated day-to-day variability of AOT follows synoptic scale advection of humidity rather than particle concentration. Even for relatively dry conditions AOT appears to be strongly influenced by the diurnal cycle of RH in the lower boundary layer, further enhanced by uptake and release of nitric acid and ammonia by aerosol water.

  7. 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.

  8. 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.

  9. Chemical and microphysical properties of the aerosol during foggy and nonfoggy episodes: a relationship between organic and inorganic content of the aerosol

    Science.gov (United States)

    Kaul, D. S.; Gupta, T.; Tripathi, S. N.

    2012-06-01

    An extensive field measurement during winter was carried out at a site located in the Indo-Gangetic Plain (IGP) which gets heavily influenced by the fog during winter almost every year. The chemical and microphysical properties of the aerosols during foggy and nonfoggy episodes and chemical composition of the fogwater are presented. Positive matrix factorization (PMF) as a tool for the source apportionment was employed to understand the sources of pollution. Four major sources viz. biomass burning, refractory, secondary and mineral dust were identified. Aerosols properties during foggy episodes were heavily influenced by almost all the sources and they caused considerable loading of almost all the organic and inorganic species during the period. The biomass generated aerosols were removed from the atmosphere by scavenging during foggy episodes. The wet removal of almost all the species by the fog droplets was observed. The K+, water soluble organic carbon (WSOC), water soluble inorganic carbon (WSIC) and NO3- were most heavily scavenged among the species and their concentrations consequently became lower than the nonfoggy episode concentrations. The production of secondary inorganic aerosol, mainly sulfate and ammonium, during foggy episodes was considerably higher than nitrate which was rather heavily scavenged and removed by the fog droplets. The fogwater analysis showed that dissolved inorganic species play a vital role in processing of organic carbon such as the formation of organo-sulfate and organo-nitrate inside the fog droplets. The formation of organo-sulfate and organo-nitrate in aerosol and the influence of acidity on the secondary organic aerosol (SOA) formation were rather found to be negligible. The study average inorganic component of the aerosol was considerably higher than the carbonaceous component during both foggy and nonfoggy episode. The secondary production of the aerosol changed the microphysical properties of aerosol which was reflected by

  10. Study of photolytic aerosols at stratospheric pressures

    International Nuclear Information System (INIS)

    Delattre, Patrick.

    1975-07-01

    An experimental study of photolytic aerosol formation at stratospheric pressure (60 Torr) and laboratory temperature, was carried out previous to the exact simulation of photolytic aerosol formation in real stratospheric conditions. An experimental simulation device, techniques of generation of known mixtures of inert gases with SO 2 and NOsub(x) traces at low concentration (below 1 ppm volume) and H 2 O traces (a few ppm), and techniques for the determination and counting of aerosol particles at low pressures were perfected. The following results were achieved: the rate of vapor condensation on nuclei was reduced when total pressure decreased. At low pressure the working of condensation nuclei counters and the formation of photolytic aerosols is influenced by this phenomenon. An explanation is proposed, as well as means to avoid this unpleasant effect on the working of nuclei counters at low pressure. No photolytic aerosol production was ascertained at 60 Torr when water concentration was below 100 ppm whatever the concentration of SO 2 or NOsub(x) traces. With water concentration below 1200ppm and SO 2 trace concentration below 1ppm, the aerosol particles produced could not consist of sulfuric acid drops but probably of nitrosyl sulfate acide crystals [fr

  11. The physico-chemical evolution of atmospheric aerosols and the gas-particle partitioning of inorganic aerosol during KORUS-AQ

    Science.gov (United States)

    Lee, T.; Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Park, J. S.; Soo, C. J.; Desyaterik, Y.; Collett, J. L., Jr.

    2017-12-01

    Aerosols influence climate change directly by scattering and absorption and indirectly by acting as cloud condensation nuclei and some of the effects of aerosols are reduction in visibility, deterioration of human health, and deposition of pollutants to ecosystems. Urban area is large source of aerosols and aerosol precursors. Aerosol sources are both local and from long-range transport. Long-range transport processed aerosol are often dominant sources of aerosol pollution in Korea. To improve our knowledge of aerosol chemistry, Korea and U.S-Air Quality (KORUS-AQ) of Aircraft-based aerosol measurement took place in and around Seoul, Korea during May and June 2016. KORUS-AQ campaigns were conducted to study the chemical characterization and processes of pollutants in the Seoul Metropolitan area to regional scales of Korean peninsula. Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on aircraft platforms on-board DC-8 (NASA) aircraft. We characterized aerosol chemical properties and mass concentrations of sulfate, nitrate, ammonium and organics in polluted air plumes and investigate the spatial and vertical distribution of the species. The results of studies show that organics is predominant in Aerosol and a significant fraction of the organics is oxygenated organic aerosol (OOA) at the high altitude. Both Nitrate and sulfate can partition between the gas and particle phases. The ratios for HNO3/(N(V) (=gaseous HNO3 + particulate Nitrate) and SO2/(SO2+Sulfate) were found to exhibit quite different distributions between the particles and gas phase for the locations during KORUS-AQ campaign, representing potential for formation of additional particulate nitrate and sulfate. The results of those studies can provide highly resolved temporal and spatial air pollutant, which are valuable for air quality model input parameters for aerosol behaviour.

  12. 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

  13. Climate forcing by anthropogenic aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Charlson, R J; Schwartz, S E; Hales, J M; Cess, R D; Coakley, Jr, J A; Hansen, J E; Hofmann, D J [University of Washington, Seattle, WA (USA). Inst. for Environmental Studies, Dept. of Atmospheric Sciences

    1992-01-24

    Although long considered to be of marginal importance to global climate change, tropospheric aerosol contributes substantially to radiative forcing, and anthropogenic sulfate aerosol in particular has imposed a major perturbation to this forcing. Both the direct scattering of short wavelength solar radiation and the modification of the shortwave reflective properties of clouds by sulfate aerosol particles increase planetary albedo, thereby exerting a cooling influence on the planet. Current climate forcing due to anthropogenic sulfate is estimated to be -1 to -2 watts per square metre, globally averaged. This perturbation is comparable in magnitude to current anthropogenic greenhouse gas forcing but opposite in sign. Thus, the aerosol forcing has likely offset global greenhouse warming to a substantial degree. However, differences in geographical and seasonal distributions of these forcings preclude any simple compensation. Aerosol effects must be taken into account in evaluating anthropogenic influences on past, current, and projected future climate and in formulating policy regarding controls on emission of greenhouse gases and sulfur dioxide. Resolution of such policy issues requires integrated research on the magnitude and geographical distribution of aerosol climate forcing and on the controlling chemical and physical processes. 73 refs., 4 figs., 2 tabs.

  14. Climate forcing by anthropogenic aerosols.

    Science.gov (United States)

    Charlson, R J; Schwartz, S E; Hales, J M; Cess, R D; Coakley, J A; Hansen, J E; Hofmann, D J

    1992-01-24

    Although long considered to be of marginal importance to global climate change, tropospheric aerosol contributes substantially to radiative forcing, and anthropogenic sulfate aerosol in particular has imposed a major perturbation to this forcing. Both the direct scattering of shortwavelength solar radiation and the modification of the shortwave reflective properties of clouds by sulfate aerosol particles increase planetary albedo, thereby exerting a cooling influence on the planet. Current climate forcing due to anthropogenic sulfate is estimated to be -1 to -2 watts per square meter, globally averaged. This perturbation is comparable in magnitude to current anthropogenic greenhouse gas forcing but opposite in sign. Thus, the aerosol forcing has likely offset global greenhouse warming to a substantial degree. However, differences in geographical and seasonal distributions of these forcings preclude any simple compensation. Aerosol effects must be taken into account in evaluating anthropogenic influences on past, current, and projected future climate and in formulating policy regarding controls on emission of greenhouse gases and sulfur dioxide. Resolution of such policy issues requires integrated research on the magnitude and geographical distribution of aerosol climate forcing and on the controlling chemical and physical processes.

  15. 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.

  16. 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…

  17. 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.

  18. Quantitative analysis of glycosaminoglycans, chondroitin/dermatan sulfate, hyaluronic acid, heparan sulfate, and keratan sulfate by liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Osago, Harumi; Shibata, Tomoko; Hara, Nobumasa; Kuwata, Suguru; Kono, Michihaya; Uchio, Yuji; Tsuchiya, Mikako

    2014-12-15

    We developed a method using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) with a selected reaction monitoring (SRM) mode for simultaneous quantitative analysis of glycosaminoglycans (GAGs). Using one-shot analysis with our MS/MS method, we demonstrated the simultaneous quantification of a total of 23 variously sulfated disaccharides of four GAG classes (8 chondroitin/dermatan sulfates, 1 hyaluronic acid, 12 heparan sulfates, and 2 keratan sulfates) with a sensitivity of less than 0.5 pmol within 20 min. We showed the differences in the composition of GAG classes and the sulfation patterns between porcine articular cartilage and yellow ligament. In addition to the internal disaccharides described above, some saccharides derived from the nonreducing terminal were detected simultaneously. The simultaneous quantification of both internal and nonreducing terminal saccharides could be useful to estimate the chain length of GAGs. This method would help to establish comprehensive "GAGomic" analysis of biological tissues. Copyright © 2014 Elsevier Inc. All rights reserved.

  19. Boric acid - ammonium rhodanide (nitrate, sulfate) - water system at 25 deg C

    Energy Technology Data Exchange (ETDEWEB)

    Skvortsov, V G; Molodkin, A K; Tsekhanskij, R S; Sadetdinov, Sh V; Nikonov, F V [Chuvashskij Gosudarstvennyj Pedagogicheskij Inst., Cheboksary (USSR); Universitet Druzhby Narodov, Moscow (USSR))

    1985-03-01

    Methods of isothermal solubility and refractometry have been used to establish that boric acid-ammonium rhodanite (nitrate, sulfate) - water systems are of a simple eutonic type. Rhodanide salts out boric acid, while nitrate and sulfate salt it in. The lyotropic effect referred to the volumetric share of both anion and cation increases in the series SCN/sup -/ < NO/sub 3//sup -/ < SO/sub 4//sup 2 -/.

  20. Study on the surfactants present in atmospheric aerosols collected in the Okinawa Japan

    Science.gov (United States)

    Kamegawa, A.; Kasaba, T.; Shimabukuro, W.; Arakaki, T.

    2017-12-01

    The main constituent of atmospheric aerosols is organic substances, which occupy 20 to 70% of the mass. Organic matters in the aerosols contain organic acids, protein and humic acid, which behave similar to surfactants. Since surfactants contain both hydrophobic and hydrophilic functional groups in the molecule, they can play important roles in cloud formation and can affect climate change, but detailed mechanisms and magnitude are not well understood. In addition, surfactants can cause asthma, allergy, dry eye and so on. In this study, our aim is to characterize surfactants in the aerosols collected in different seasons in Okinawa, Japan. Atmospheric aerosols were collected at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS) during Sep. 2013 and July 2014. Surfactants in the environment are comprised of artificially synthesized compounds and naturally derived organics so we only differentiate them into anionic and cationic surfactants. Colorimetric methods were used to determine the concentrations of anionic surfactants as methylene blue active substance (MBAS). Cationic surfactants were also measured by colorimetric method as disulfine blue active substance (DBAS) and showed always below detection limit. Thus, we only discuss anionic surfactants measured as MBAS. Water soluble organic carbon (WSOC) and metal concentrations were also measured for the same aerosol samples. Concentrations of MBAS in the studied samples were 2-3 times higher in spring, fall and winter than those collected in summer. MBAS concentration in the aerosols showed strong correlation with sulfate ion and WSOC, and slightly weaker correlation with nss-sulfate ion. Among the metals, only sodium ion showed a relatively strong correlation with MBAS concentrations. It is suggested that the anionic surfactants in the studied aerosols are mainly derived from marine sources.

  1. First Simulations of Designing Stratospheric Sulfate Aerosol Geoengineering to Meet Multiple Simultaneous Climate Objectives

    Science.gov (United States)

    Kravitz, Ben; MacMartin, Douglas G.; Mills, Michael J.; Richter, Jadwiga H.; Tilmes, Simone; Lamarque, Jean-Francois; Tribbia, Joseph J.; Vitt, Francis

    2017-12-01

    We describe the first simulations of stratospheric sulfate aerosol geoengineering using multiple injection locations to meet multiple simultaneous surface temperature objectives. Simulations were performed using CESM1(WACCM), a coupled atmosphere-ocean general circulation model with fully interactive stratospheric chemistry, dynamics (including an internally generated quasi-biennial oscillation), and a sophisticated treatment of sulfate aerosol formation, microphysical growth, and deposition. The objectives are defined as maintaining three temperature features at their 2020 levels against a background of the RCP8.5 scenario over the period 2020-2099. These objectives are met using a feedback mechanism in which the rate of sulfur dioxide injection at each of the four locations is adjusted independently every year of simulation. Even in the presence of uncertainties, nonlinearities, and variability, the objectives are met, predominantly by SO2 injection at 30°N and 30°S. By the last year of simulation, the feedback algorithm calls for a total injection rate of 51 Tg SO2 per year. The injections are not in the tropics, which results in a greater degree of linearity of the surface climate response with injection amount than has been found in many previous studies using injection at the equator. Because the objectives are defined in terms of annual mean temperature, the required geongineering results in "overcooling" during summer and "undercooling" during winter. The hydrological cycle is also suppressed as compared to the reference values corresponding to the year 2020. The demonstration we describe in this study is an important step toward understanding what geoengineering can do and what it cannot do.

  2. 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.

  3. The boric acid - ammonium rhodanide (nitrate, sulfate) - water system at 25 deg C

    International Nuclear Information System (INIS)

    Skvortsov, V.G.; Molodkin, A.K.; Tsekhanskij, R.S.; Sadetdinov, Sh.V.; Nikonov, F.V.

    1985-01-01

    Methods of isothermal solubility and refractometry have been used to establish that boric acid-ammonium rhodanite (nitrate, sulfate) - water systems are of a simple eutonic type. Rhodanide salts out boric acid, while nitrate and sulfate salt it in. The lyotropic effect referred to the volumetric share of both anion and cation increases in the series SCN - 3 - 4 2-

  4. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Science.gov (United States)

    Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2018-04-01

    While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  5. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Directory of Open Access Journals (Sweden)

    B. Jing

    2018-04-01

    Full Text Available While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO32 and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA. The nitrate salt ∕ organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH, the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  6. Enhancement of carboxylic acid degradation with sulfate radical generated by persulfate activation.

    Science.gov (United States)

    Criquet, J; Nebout, P; Karpel Vel Leitner, N

    2010-01-01

    The aim of this work was to investigate the generation of sulfate radical for the removal of two carboxylic acids in aqueous solution: acetic and citric acids. From photochemical and radiolytic processes, kinetics of the degradation of these two carboxylic acids was studied as a function of the pH of the solution. It was shown that the maximum of acetic acid degradation occurred at pH 5. Above this pH, competitive reactions with the carbon mineralized inhibit the reaction of with the solute. In the case of citric acid, pH has only a little effect on the kinetic of citric acid degradation. The determination of mineralization yields shows several differences depending on carboxylic acids and pH. The degradation of both carboxylic acids was also studied in the radiolysis process whether with or without persulfate addition. A comparison of the processes of sulfate radical production is presented.

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

    Directory of Open Access Journals (Sweden)

    E. A. Marais

    2016-02-01

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

  8. Physicochemical characteristics of chlorofluorohydrocarbon-based inhalation aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Ashurst, I C

    1985-01-01

    The aim of this work was to gain a better understanding of the physicochemical factors which affect the formulation of suspension inhalation aerosols. The adsorption of six nonionic and cationic surfactants onto Spherisorb has been investigated. The results were analyzed by calculating the area occupied by one adsorbed molecule at the surface and by comparing these values for each surfactant. The amount of each surfactant adsorbed was correlated with the number of sites on that surfactant molecule which could interact with the surface. The stability of suspensions, produced by both the model colloid Spherisorb, and by the drug isoprenaline sulfate, after adsorption of the surfactants, has been assessed by measuring settling times and rising times. The most stable suspension were found to be those which had the greatest amounts of long chain fatty acid surfactant adsorbed on their surface. A comparison was made between the effective stabilizing properties of Span 85 and oleic acid on various drug suspension. It was found that Span 85 gave the most stable suspension. Inhalation aerosol suspensions of isoprenaline sulfate were manufactured using the same surfactants used in the adsorption and suspension stability studies and were analyzed by measuring the particle size distributions of the suspension and the emitted doses. The results were found to correlate with the adsorption and suspension stability studies and it was concluded that a deflocculated suspension was preferable to a flocculated suspension in inhalation aerosols provided that the drug density was less than the propellant density. The application of this work to preformulation studies was also discussed.

  9. Optical properties of the urban aerosol and their relation to chemical composition

    International Nuclear Information System (INIS)

    Leaderer, B.P.; Stolwijk, J.A.J.

    1980-01-01

    Light extinction and resulting visibility degradation in an unsaturated precipitation-free atmosphere are determined by light absorption and scattering and are caused by a complex mix of natural components and anthropogenic pollutants. The paper reviews correlation studies relating light scattering and light extinction (visibility) to concentrations of sulfate mass, nitrate mass, the remainder of the mass, and in some cases organic aerosol mass, while accounting for variations in relative humidity. It is found that sulfate aerosol mass is the dominant chemical aerosol species affecting light scattering and extinction. The dominant effect of sulfate mass on light scattering and extinction, even when sulfates account for a relatively small fraction of the total mass, results from the fact that sulfates are secondary aerosols and are mostly found in the 0.1-1.0 micron size range

  10. Characterisation of boric acid aerosol behaviour and interactions with stainless steel

    International Nuclear Information System (INIS)

    Anderson, A.B.; Beard, A.M.; Bennett, P.J.; Benson, C.G.

    1991-03-01

    Experiments have been conducted to determine the physical characteristics of boric acid aerosol. Aqueous solutions of boric acid (either 200 or 2000 ppm boron) were injected at a controlled rate onto a 304 stainless steel cone held at 1000 o C. The transport and deposition of the resulting aerosol was studied through a system including pipework and a dilution chamber. Work was also undertaken to characterise the interaction between boric acid and stainless steel. Boric acid was vaporized in steam-argon atmospheres at 300 o C and passed over 304 stainless steel coupons held at temperatures between 400 and 1000 o C. (author)

  11. 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.

  12. Hydrophobic interactions between polymethacrylic acid and sodium laureth sulfate in aqueous solutions

    Science.gov (United States)

    Yaremko, Z. M.; Fedushinskaya, L. B.; Burka, O. A.; Soltys, M. N.

    2014-09-01

    The role of hydrophobic interaction in the development of associative processes is demonstrated, based on the concentration dependences of the viscosity and pH of binary solutions of polymethacrylic acid as an anionic polyelectrolyte and sodium laureth sulfate as an anionic surfactant. It is found that the inflection point on the dependence of the difference between the pH values of binary solutions of polymethacrylic acid and sodium laureth sulfate on the polyelectrolyte concentration is a criterion for determining the predominant contribution from hydrophobic interaction, as is the inflection point on the dependence of pH of individual solutions of polymethacrylic acid on the polyelectrolyte concentration.

  13. Chemical Thermodynamics of Aqueous Atmospheric Aerosols: Modeling and Microfluidic Measurements

    Science.gov (United States)

    Nandy, L.; Dutcher, C. S.

    2017-12-01

    Accurate predictions of gas-liquid-solid equilibrium phase partitioning of atmospheric aerosols by thermodynamic modeling and measurements is critical for determining particle composition and internal structure at conditions relevant to the atmosphere. Organic acids that originate from biomass burning, and direct biogenic emission make up a significant fraction of the organic mass in atmospheric aerosol particles. In addition, inorganic compounds like ammonium sulfate and sea salt also exist in atmospheric aerosols, that results in a mixture of single, double or triple charged ions, and non-dissociated and partially dissociated organic acids. Statistical mechanics based on a multilayer adsorption isotherm model can be applied to these complex aqueous environments for predictions of thermodynamic properties. In this work, thermodynamic analytic predictive models are developed for multicomponent aqueous solutions (consisting of partially dissociating organic and inorganic acids, fully dissociating symmetric and asymmetric electrolytes, and neutral organic compounds) over the entire relative humidity range, that represent a significant advancement towards a fully predictive model. The model is also developed at varied temperatures for electrolytes and organic compounds the data for which are available at different temperatures. In addition to the modeling approach, water loss of multicomponent aerosol particles is measured by microfluidic experiments to parameterize and validate the model. In the experimental microfluidic measurements, atmospheric aerosol droplet chemical mimics (organic acids and secondary organic aerosol (SOA) samples) are generated in microfluidic channels and stored and imaged in passive traps until dehydration to study the influence of relative humidity and water loss on phase behavior.

  14. 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

    2007-06-01

    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 predominantly 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 was 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 throughout all altitudes within the boundary layer (altitude less than 2.5 km, but was significantly higher at altitude layers 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

  15. 75 FR 78243 - Propionic Acid and Salts, Urea Sulfate, Methidathion, and Methyl Parathion; Registration Review...

    Science.gov (United States)

    2010-12-15

    ... ENVIRONMENTAL PROTECTION AGENCY [EPA-HQ-OPP-2010-0650; FRL-8855-5] Propionic Acid and Salts, Urea.... 4078, urea sulfate, case no. 7213, methidathion, case no. 0034, and methyl parathion, case no. 0153... pesticides in the table below--propionic acid and salts, case 4078, urea sulfate, case no. 7213, methidathion...

  16. Field and Laboratory Studies of Atmospheric Organic Aerosol

    Science.gov (United States)

    Coggon, Matthew Mitchell

    of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( 4 hr). Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate. Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

  17. An interfacial mechanism for cloud droplet formation on organic aerosols.

    Science.gov (United States)

    Ruehl, Christopher R; Davies, James F; Wilson, Kevin R

    2016-03-25

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation. Copyright © 2016, American Association for the Advancement of Science.

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

    International Nuclear Information System (INIS)

    Sánchez-Andrea, Irene; Sanz, Jose Luis; Bijmans, Martijn F.M.; Stams, Alfons J.M.

    2014-01-01

    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

  19. 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.

  20. Engineering assessment of in situ sulfate production onboard aircraft at high altitude

    Science.gov (United States)

    Smith, J.; Dykema, J. A.; Keith, D.

    2016-12-01

    Stratospheric injection of scattering aerosols has been proposed as a way to reduce global temperature increases by decreasing net atmospheric radiative forcing. Several methods have been suggested as a means of implementing solar geoengineering, and high altitude aircraft have been identified as an accessible means delivering sulfate aerosols to the lower and mid-stratosphere. This research initiative analyzes the design features of an onboard open cycle chemical plant capable of in situ sulfur to sulfate conversion, and compares the required mass to that of transporting pre-fabricated gaseous or liquid sulfate aerosol precursors. Scaling from aero-derivative gas turbine engines, commercial catalytic converters, and existing aerospace materials indicate that aircraft equipped with such a system could provide a substantial mass benefit compared to direct transport of compound sulfate products.

  1. A unified approach to infrared aerosol remote sensing and type specification

    Directory of Open Access Journals (Sweden)

    L. Clarisse

    2013-02-01

    Full Text Available Atmospheric aerosols impact air quality and global climate. Space based measurements are the best way to observe their spatial and temporal distributions, and can also be used to gain better understanding of their chemical, physical and optical properties. Aerosol composition is the key parameter affecting the refractive index, which determines how much radiation is scattered and absorbed. Composition of aerosols is unfortunately not measured by state of the art satellite remote sounders. Here we use high resolution infrared measurements for aerosol type differentiation, exploiting, in that part of spectrum, the dependency of their refractive index on wavelength. We review existing detection methods and present a unified detection method based on linear discrimination analysis. We demonstrate this method on measurements of the Infrared Atmospheric Sounding Interferometer (IASI and five different aerosol types, namely volcanic ash, windblown sand, sulfuric acid droplets, ammonium sulfate and smoke particles. We compare these with traditional MODIS AOD measurements. The detection of the last three types is unprecedented in the infrared in nadir mode, but is very promising, especially for sulfuric acid droplets which are detected in the lower troposphere and up to 6 months after injection in the upper troposphere/lower stratosphere.

  2. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  3. Lipid organics in background aerosols, cloudwater, and snow and implication for organic scavenging

    International Nuclear Information System (INIS)

    Groellert, C.

    1998-01-01

    During three years free tropospheric snow, aerosol, and cloudwater samples were collected at Mount Sonnblick, Austria, at an elevation of 3106 m a.s.l. The samples were analyzed for their lipid organic trace components using extraction with n-hexane as sample pretreatment and gas chromatography-mass spectrometry-flame ionization detection for identification and quantification of the substances. The main components identified in all the samples were the phthalic acid esters which are of anthropogenic origin. Of further interest were aliphatic alcohols (not detected in aerosols) and phenols. They are of biogenic origin. The concentrations were found to be higher in spring than in the fall season. To compare the concentrations of aerosol, cloudwater and snow samples scavenging ratios (aerosol to snow), scavenging efficiencies (aerosol to cloud) and cloud to snow ratios were calculated for the first time for organic compounds. Scavenging ratios were 10 to 100 times lower, scavenging efficiencies 2 to 10 times lower than sulfate. This can result from the poor watersolubility of the compounds or from gas phase sorptions on the filter surface (overestimation of aerosol concentrations). The cloud to snow ratios were generally higher than for sulfate. However, a few components exhibited very low cloud to snow ratios which might be due to additional sources in snow for these substances (alcohols). (author)

  4. Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO2

    Directory of Open Access Journals (Sweden)

    T. Liu

    2016-01-01

    Full Text Available Sulfur dioxide (SO2 can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs, but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs, formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60–200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97 between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS resolved OA's relatively lower oxygen-to-carbon (O : C (0.44 ± 0.02 and higher hydrogen-to-carbon (H : C (1.40 ± 0.03 molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc of −0.51 ± 0.06 than −0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

  5. A study of diurnal variations of PM2.5 acidity and related chemical species using a new thermodynamic equilibrium model

    International Nuclear Information System (INIS)

    Behera, Sailesh N.; Betha, Raghu; Liu, Ping; Balasubramanian, Rajasekhar

    2013-01-01

    Aerosol acidity is one of the most important parameters that can influence atmospheric visibility, climate change and human health. Based on continuous field measurements of inorganic aerosol species and their thermodynamic modeling on a time resolution of 1 h, this study has investigated the acidic properties of PM 2.5 and their relation with the formation of secondary inorganic aerosols (SIA). The study was conducted by taking into account the prevailing ambient temperature (T) and relative humidity (RH) in a tropical urban atmosphere. The in-situ aerosol pH (pH IS ) on a 12 h basis ranged from − 0.20 to 1.46 during daytime with an average value of 0.48 and 0.23 to 1.53 during nighttime with an average value of 0.72. These diurnal variations suggest that the daytime aerosol was more acidic than that caused by the nighttime aerosol. The hourly values of pH IS showed a reverse trend as compared to that of in-situ aerosol acidity ([H + ] Ins ). The pH IS had its maximum values at 3:00 and at 20:00 and its minimum during 11:00 to 12:00. Correlation analyses revealed that the molar concentration ratio of ammonium to sulfate (R N/S ), equivalent concentration ratio of cations to anions (R C/A ), T and RH can be used as independent variables for prediction of pH IS . A multi-linear regression model consisting of R N/S , R C/A, T and RH was developed to estimate aerosol pH IS. - Highlights: • Fine aerosol acidic characteristics were evaluated on an hourly basis. • Diurnal variations of in-situ acidity, water content and pH of aerosols were investigated. • Aerosols were more acidic during daytime than during nighttime. • The molar ratio of ammonium to sulfate and equivalent ratio of cations to anions were good indicators of aerosol acidity. • Meteorology had a significant effect on the hygroscopic nature of aerosol

  6. Attachment behavior of fission products to solution aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Takamiya, Koichi; Tanaka, Toru; Nitta, Shinnosuke; Itosu, Satoshi; Sekimoto, Shun; Oki, Yuichi; Ohtsuki, Tsutomu [Research Reactor Institute, Kyoto University, Osaka (Japan)

    2016-12-15

    Various characteristics such as size distribution, chemical component and radioactivity have been analyzed for radioactive aerosols released from Fukushima Daiichi Nuclear Power Plant. Measured results for radioactive aerosols suggest that the potential transport medium for radioactive cesium was non-sea-salt sulfate. This result indicates that cesium isotopes would preferentially attach with sulfate compounds. In the present work the attachment behavior of fission products to aqueous solution aerosols of sodium salts has been studied using a generation system of solution aerosols and spontaneous fission source of {sup 248}Cm. Attachment ratios of fission products to the solution aerosols were compared among the aerosols generated by different solutions of sodium salt. A significant difference according as a solute of solution aerosols was found in the attachment behavior. The present results suggest the existence of chemical effects in the attachment behavior of fission products to solution aerosols.

  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. Liquid-liquid phase separation in internally mixed magnesium sulfate/glutaric acid particles

    Science.gov (United States)

    Wu, Feng-Min; Wang, Xiao-Wei; Jing, Bo; Zhang, Yun-Hong; Ge, Mao-Fa

    2018-04-01

    The confocal Raman microscopy is utilized to investigate the liquid-liquid phase separation (LLPS) of mixed magnesium sulfate/glutaric acid (MgSO4/GA) droplets deposited on a hydrophobic polytetrafluoroethylene (PTFE) substrate and a hydrophilic quartz substrate. Raman spectra collected from different regions of the mixed droplets provide detailed information of component distributions for MgSO4 and GA. During the dehydration process, the MgSO4/GA mixed particles show the initial liquid-liquid phase separation between 85% and 80% relative humidity (RH) on both the hydrophobic and hydrophilic substrates. For the droplets deposited on the two substrates, the inner phase of droplets is dominated by aqueous MgSO4, which is surrounded by a rich GA organic layer due to the surface tension effects. In addition, the crystallization of GA could be observed in the organic aqueous phase while it is inhibited in the inner MgSO4 phase due to the effects of gel formation of MgSO4 at low RH. The Raman spectra reveal that with decreasing RH the morphology of the mixed droplet evolves from a uniform droplet to the structure of LLPS with the GA crystallizing in the outer layer and MgSO4 gel formed in the inner phase. These findings contribute to the further understanding of the role of interactions between inorganic salts and organic acids on the morphological evolution and environmental effects of atmospheric aerosols under ambient RH conditions.

  9. Possible influence of anthropogenic aerosols on cirrus clouds and anthropogenic forcing

    Directory of Open Access Journals (Sweden)

    J. E. Penner

    2009-02-01

    Full Text Available Cirrus clouds have a net warming effect on the atmosphere and cover about 30% of the Earth's area. Aerosol particles initiate ice formation in the upper troposphere through modes of action that include homogeneous freezing of solution droplets, heterogeneous nucleation on solid particles immersed in a solution, and deposition nucleation of vapor onto solid particles. Here, we examine the possible change in ice number concentration from anthropogenic soot originating from surface sources of fossil fuel and biomass burning, from anthropogenic sulfate aerosols, and from aircraft that deposit their aerosols directly in the upper troposphere. We use a version of the aerosol model that predicts sulfate number and mass concentrations in 3-modes and includes the formation of sulfate aerosol through homogeneous binary nucleation as well as a version that only predicts sulfate mass. The 3-mode version best represents the Aitken aerosol nuclei number concentrations in the upper troposphere which dominated ice crystal residues in the upper troposphere. Fossil fuel and biomass burning soot aerosols with this version exert a radiative forcing of −0.3 to −0.4 Wm−2 while anthropogenic sulfate aerosols and aircraft aerosols exert a forcing of −0.01 to 0.04 Wm−2 and −0.16 to −0.12 Wm−2, respectively, where the range represents the forcing from two parameterizations for ice nucleation. The sign of the forcing in the mass-only version of the model depends on which ice nucleation parameterization is used and can be either positive or negative. The magnitude of the forcing in cirrus clouds can be comparable to the forcing exerted by anthropogenic aerosols on warm clouds, but this forcing has not been included in past assessments of the total anthropogenic radiative forcing of climate.

  10. Aerosol Mass Scattering Efficiency: Generalized Treatment of the Organic Fraction

    Science.gov (United States)

    Garland, R. M.; Ravishankara, A. R.; Lovejoy, E. R.; Tolbert, M. A.; Baynard, T.

    2005-12-01

    Atmospheric aerosols are complex mixtures of organic and inorganic compounds. Current efforts to provide a simplified parameterization to describe the RH dependence of water uptake and associated optical properties lack the capability to include any dependence on the composition of the organic fraction. Using laboratory generated aerosol we have investigated the validity of such simplified treatment of organic fraction and estimated potential biases. In this study, we use cavity ring-down aerosol extinction photometry (CRD-AEP) to study the relative humidity (RH) dependence of the light extinction of aerosols, σep, simultaneously considering the influence of particle size, chemical composition, and mixing state (internal and external mixtures). We have produced internally mixed aerosol systems including; ammonium sulfate, ammonium nitrate, sodium chloride, dicarboxylic acids, sugars, amino acids and humic acid. These aerosols are produced with an atomizer and size-selected with a Differential Mobility Analyzer (DMA). The particles then enter into a CRD-AEP to measure dry extinction, σep(Dry), after which they travel into a RH conditioner and another CRD-AEP to measure the humidified aerosol extinction, fσ(ep)RH. The ratio of the humidified extinction to the dry extinction is fσ(ep)RH. Representative organic compounds were found to have fσ(ep)RH values that are much smaller than pure salts; though the fσ(ep)RH values vary little within the organic compounds studied. In addition, we have found that treating the inorganic/organic aerosols as external mixtures is generally correct to within ~10%, indicating appropriate simplified treatment of the RH dependence of atmospheric aerosol according to inorganic/organic fraction. In this presentation, we include recommendations for the generalized treatment of the organic fraction, exceptions to this generalized behavior, and estimates of the potential bias caused by generalized treatment.

  11. Tillage and water management for riceland productivity in acid sulfate soils of the Mekong delta, Vietnam.

    NARCIS (Netherlands)

    Minh, L.Q.; Tuong, T.P.; Mensvoort, van M.E.F.; Bouma, J.

    1997-01-01

    Acid sulfate soils are characterized by low pH and high concentrations of aluminum, sulfate, iron and hydrogen sulfide. Removal of at least part of these substances is a prerequisite for land use, at least in severely acid soils. In this study, the effectiveness of harrowing and flushing with

  12. Aerosol composition and sources during the Chinese Spring Festival: fireworks, secondary aerosol, and holiday effects

    Science.gov (United States)

    Jiang, Q.; Sun, Y. L.; Wang, Z.; Yin, Y.

    2015-06-01

    Aerosol particles were characterized by an Aerodyne aerosol chemical speciation monitor along with various collocated instruments in Beijing, China, to investigate the role of fireworks (FW) and secondary aerosol in particulate pollution during the Chinese Spring Festival of 2013. Three FW events, exerting significant and short-term impacts on fine particles (PM2.5), were observed on the days of Lunar New Year, Lunar Fifth Day, and Lantern Festival. The FW were shown to have a large impact on non-refractory potassium, chloride, sulfate, and organics in submicron aerosol (PM1), of which FW organics appeared to be emitted mainly in secondary, with its mass spectrum resembling that of secondary organic aerosol (SOA). Pollution events (PEs) and clean periods (CPs) alternated routinely throughout the study. Secondary particulate matter (SPM = SOA + sulfate + nitrate + ammonium) dominated the total PM1 mass on average, accounting for 63-82% during nine PEs in this study. The elevated contributions of secondary species during PEs resulted in a higher mass extinction efficiency of PM1 (6.4 m2 g-1) than during CPs (4.4 m2 g-1). The Chinese Spring Festival also provides a unique opportunity to study the impact of reduced anthropogenic emissions on aerosol chemistry in the city. Primary species showed ubiquitous reductions during the holiday period with the largest reduction being in cooking organic aerosol (OA; 69%), in nitrogen monoxide (54%), and in coal combustion OA (28%). Secondary sulfate, however, remained only slightly changed, and the SOA and the total PM2.5 even slightly increased. Our results have significant implications for controlling local primary source emissions during PEs, e.g., cooking and traffic activities. Controlling these factors might have a limited effect on improving air quality in the megacity of Beijing, due to the dominance of SPM from regional transport in aerosol particle composition.

  13. Post-flame gas-phase sulfation of potassium chloride

    DEFF Research Database (Denmark)

    Li, Bo; Sun, Zhiwei; Li, Zhongshan

    2013-01-01

    The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously homogene......The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously...

  14. Uptake of Alkylamines on Dicarboxylic Acids Relevant to Secondary Organic Aerosol Formation

    Science.gov (United States)

    Marrero-Ortiz, W.; Secrest, J.; Zhang, R.

    2017-12-01

    Aerosols play a critical role in climate directly by scattering and absorbing solar radiation, and indirectly by functioning as cloud condensation nuclei (CCN); both represent the largest uncertainties in climate predictions. New particle formation contributes significantly to CCN production; however, the mechanisms related to particle nucleation and growth processes are not well understood. Organic acids are atmospherically abundant, and their neutralization by low molecular weight amines may result in the formation of stable low volatility aminium salt products contributing to the growth of secondary organic aerosols and even the alteration of the aerosol properties. The acid-base neutralization of particle phase succinic acid and tartaric acid by low molecular weight aliphatic amines, i.e. methylamine, dimethylamine, and trimethylamine, has been investigated by employing a low-pressure fast flow reactor at 298K with an ion drift - chemical ionization mass spectrometer (ID-CIMS). The heterogeneous uptake is time dependent and influenced by organic acids functionality, alkylamines basicity, and steric effect. The implications of our results to atmospheric nanoparticle growth will be discussed.

  15. Photothermal spectroscopy of aerosols

    International Nuclear Information System (INIS)

    Campillo, A.J.; Lin, H.B.

    1981-04-01

    In situ aerosol absorption spectroscopy was performed using two novel photothermal detection schemes. The first, based on a photorefractive effect and coherent detection, called phase fluctuation optical heterodyne (PFLOH) spectroscopy, could, depending on the geometry employed, yield particle specific or particle and gas absorption data. Single particles of graphite as small as 1 μm were detected in the particle specific mode. In another geometrical configuration, the total absorption (both gas and particle) of submicron sized aerosols of ammonium sulfate particles in equilibrium with gaseous ammonia and water vapor were measured at varying CO 2 laser frequencies. The specific absorption coefficient for the sulfate ion was measured to be 0.5 m 2 /g at 1087 cm -1 . The absorption coefficient sensitivity of this scheme was less than or equal to 10 -8 cm -1 . The second scheme is a hybrid visible Mie scattering scheme incorporating photothermal modulation. Particle specific data on ammonium sulfate droplets were obtained. For chemically identical species, the relative absorption spectrum versus laser frequency can be obtained for polydisperse aerosol distributions directly from the data without the need for complex inverse scattering calculations

  16. Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

    Science.gov (United States)

    Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

    2017-12-01

    Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

  17. Separation and Precipitation of Nickel from Acidic Sulfate Leaching Solution of Molybdenum-Nickel Black Shale by Potassium Nickel Sulfate Hexahydrate Crystallization

    Science.gov (United States)

    Deng, Zhigan; Wei, Chang; Fan, Gang; Li, Xingbin; Li, Minting; Li, Cunxiong

    2018-02-01

    Nickel was separated and precipitated with potassium nickel sulfate hexahydrate [K2Ni(SO4)2·6H2O] from acidic sulfate solution, a leach solution from molybdenum-nickel black shale. The effects of the potassium sulfate (K2SO4) concentration, crystallization temperature, solution pH, and crystallization time on nickel(II) recovery and iron(III) precipitation were investigated, revealing that nickel and iron were separated effectively. The optimum parameters were K2SO4 concentration of 200 g/L, crystallization temperature of 10°C, solution pH of 0.5, and crystallization time of 24 h. Under these conditions, 97.6% nickel(II) was recovered as K2Ni(SO4)2·6H2O crystals while only 2.0% of the total iron(III) was precipitated. After recrystallization, 98.4% pure K2Ni(SO4)2·6H2O crystals were obtained in the solids. The mother liquor was purified by hydrolysis-precipitation followed by cooling, and more than 99.0% K2SO4 could be crystallized. A process flowsheet was developed to separate iron(III) and nickel(II) from acidic-sulfate solution.

  18. Sulfate Aerosols from Non-Explosive Volcanoes: Chemical-Radiative Effects in the Troposphere and Lower Stratosphere

    Directory of Open Access Journals (Sweden)

    Giovanni Pitari

    2016-06-01

    Full Text Available SO2 and H2S are the two most important gas-phase sulfur species emitted by volcanoes, with a global amount from non-explosive emissions of the order 10 Tg-S/yr. These gases are readily oxidized forming SO42− aerosols, which effectively scatter the incoming solar radiation and cool the surface. They also perturb atmospheric chemistry by enhancing the NOx to HNO3 heterogeneous conversion via hydrolysis on the aerosol surface of N2O5 and Br-Cl nitrates. This reduces formation of tropospheric O3 and the OH to HO2 ratio, thus limiting the oxidation of CH4 and increasing its lifetime. In addition to this tropospheric chemistry perturbation, there is also an impact on the NOx heterogeneous chemistry in the lower stratosphere, due to vertical transport of volcanic SO2 up to the tropical tropopause layer. Furthermore, the stratospheric O3 formation and loss, as well as the NOx budget, may be slightly affected by the additional amount of upward diffused solar radiation and consequent increase of photolysis rates. Two multi-decadal time-slice runs of a climate-chemistry-aerosol model have been designed for studying these chemical-radiative effects. A tropopause mean global net radiative flux change (RF of −0.23 W·m−2 is calculated (including direct and indirect aerosol effects with a 14% increase of the global mean sulfate aerosol optical depth. A 5–15 ppt NOx decrease is found in the mid-troposphere subtropics and mid-latitudes and also from pole to pole in the lower stratosphere. The tropospheric NOx perturbation triggers a column O3 decrease of 0.5–1.5 DU and a 1.1% increase of the CH4 lifetime. The surface cooling induced by solar radiation scattering by the volcanic aerosols induces a tropospheric stabilization with reduced updraft velocities that produce ice supersaturation conditions in the upper troposphere. A global mean 0.9% decrease of the cirrus ice optical depth is calculated with an indirect RF of −0.08 W·m−2.

  19. MIRAGE: Model description and evaluation of aerosols and trace gases

    Science.gov (United States)

    Easter, Richard C.; Ghan, Steven J.; Zhang, Yang; Saylor, Rick D.; Chapman, Elaine G.; Laulainen, Nels S.; Abdul-Razzak, Hayder; Leung, L. Ruby; Bian, Xindi; Zaveri, Rahul A.

    2004-10-01

    The Model for Integrated Research on Atmospheric Global Exchanges (MIRAGE) modeling system, designed to study the impacts of anthropogenic aerosols on the global environment, is described. MIRAGE consists of a chemical transport model coupled online with a global climate model. The chemical transport model simulates trace gases, aerosol number, and aerosol chemical component mass (sulfate, methane sulfonic acid (MSA), organic matter, black carbon (BC), sea salt, and mineral dust) for four aerosol modes (Aitken, accumulation, coarse sea salt, and coarse mineral dust) using the modal aerosol dynamics approach. Cloud-phase and interstitial aerosol are predicted separately. The climate model, based on Community Climate Model, Version 2 (CCM2), has physically based treatments of aerosol direct and indirect forcing. Stratiform cloud water and droplet number are simulated using a bulk microphysics parameterization that includes aerosol activation. Aerosol and trace gas species simulated by MIRAGE are presented and evaluated using surface and aircraft measurements. Surface-level SO2 in North American and European source regions is higher than observed. SO2 above the boundary layer is in better agreement with observations, and surface-level SO2 at marine locations is somewhat lower than observed. Comparison with other models suggests insufficient SO2 dry deposition; increasing the deposition velocity improves simulated SO2. Surface-level sulfate in North American and European source regions is in good agreement with observations, although the seasonal cycle in Europe is stronger than observed. Surface-level sulfate at high-latitude and marine locations, and sulfate above the boundary layer, are higher than observed. This is attributed primarily to insufficient wet removal; increasing the wet removal improves simulated sulfate at remote locations and aloft. Because of the high sulfate bias, radiative forcing estimates for anthropogenic sulfur given in 2001 by S. J. Ghan and

  20. Sulfation of chondroitin. Specificity, degree of sulfation, and detergent effects with 4-sulfating and 6-sulfating microsomal systems

    International Nuclear Information System (INIS)

    Sugumaran, G.; Silbert, J.E.

    1988-01-01

    Microsomal preparations from chondroitin 6-sulfate-producing chick embryo epiphyseal cartilage, and from chondroitin 4-sulfate-producing mouse mastocytoma cells, were incubated with UDP-[14C]glucuronic acid and UDP-N-acetylgalactosamine to form non-sulfated proteo[14C]chondroitin. Aliquots of the incubations were then incubated with 3'-phosphoadenylylphosphosulfate (PAPS) in the presence or absence of various detergents. In the absence of detergents, there was good sulfation of this endogenous proteo[14C]chondroitin by the original microsomes from both sources. Detergents, with the exception of Triton X-100, markedly inhibited sulfation in the mast cell system but not in the chick cartilage system. These results indicate that sulfation and polymerization are closely linked on cell membranes and that in some cases this organization can be disrupted by detergents. When aliquots of the original incubation were heat inactivated, and then reincubated with new microsomes from chick cartilage and/or mouse mastocytoma cells plus PAPS, there was no significant sulfation of this exogenous proteo[14C] chondroitin with either system unless Triton X-100 was added. Sulfation of exogenous chondroitin and chondroitin hexasaccharide was compared with sulfation of endogenous and exogenous proteo[14C]chondroitin. Sulfate incorporation into hexasaccharide and chondroitin decreased as their concentrations (based on uronic acid) approached that of the proteo[14C]chondroitin. At the same time, the degree of sulfation in percent of substituted hexosamine increased. However, the degree of sulfation did not reach that of the endogenous proteo[14C]chondroitin. Hexasaccharide and chondroitin sulfation were stimulated by the presence of Triton X-100. However, in contrast to the exogenous proteo[14C]chondroitin, there was some sulfation of hexasaccharide and chondroitin in the absence of this detergent

  1. First Simulations of Designing Stratospheric Sulfate Aerosol Geoengineering to Meet Multiple Simultaneous Climate Objectives: DESIGNING STRATOSPHERIC GEOENGINEERING

    Energy Technology Data Exchange (ETDEWEB)

    Kravitz, Ben [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland WA USA; MacMartin, Douglas G. [Mechanical and Aerospace Engineering, Cornell University, Ithaca NY USA; Department of Computing and Mathematical Sciences, California Institute of Technology, Pasadena CA USA; Mills, Michael J. [Atmospheric Chemistry, Observations, and Modeling Laboratory, National Center for Atmospheric Research, Boulder CO USA; Richter, Jadwiga H. [Climate and Global Dynamics Laboratory, National Center for Atmospheric Research, Boulder CO USA; Tilmes, Simone [Atmospheric Chemistry, Observations, and Modeling Laboratory, National Center for Atmospheric Research, Boulder CO USA; Climate and Global Dynamics Laboratory, National Center for Atmospheric Research, Boulder CO USA; Lamarque, Jean-Francois [Atmospheric Chemistry, Observations, and Modeling Laboratory, National Center for Atmospheric Research, Boulder CO USA; Tribbia, Joseph J. [Climate and Global Dynamics Laboratory, National Center for Atmospheric Research, Boulder CO USA; Vitt, Francis [Atmospheric Chemistry, Observations, and Modeling Laboratory, National Center for Atmospheric Research, Boulder CO USA

    2017-12-07

    We describe the first simulations of stratospheric sulfate aerosol geoengineering using multiple injection locations to meet multiple simultaneous surface temperature objectives. Simulations were performed using CESM1(WACCM), a coupled atmosphere-ocean general circulation model with fully interactive stratospheric chemistry, dynamics (including an internally generated quasi-biennial oscillation), and a sophisticated treatment of sulfate aerosol formation, microphysical growth, and deposition. The objectives are defined as maintaining three temperature features at their 2020 levels against a background of the RCP8.5 scenario over the period 2020-2099. These objectives are met using a feedback mechanism in which the rate of sulfur dioxide injection at each of the four locations is adjusted independently every year of simulation. Even in the presence of uncertainties, nonlinearities, and variability, the objectives are met, predominantly by SO2 injection at 30°N and 30°S. By the last year of simulation, the feedback algorithm calls for a total injection rate of 51 Tg SO2 per year. The injections are not in the tropics, which results in a greater degree of linearity of the surface climate response with injection amount than has been found in many previous studies using injection at the equator. Because the objectives are defined in terms of annual mean temperature, the required geeongineering results in "overcooling" during summer and "undercooling" during winter. The hydrological cycle is also suppressed as compared to the reference values corresponding to the year 2020. The demonstration we describe in this study is an important step toward understanding what geoengineering can do and what it cannot do.

  2. 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.

  3. Evaluating aerosol indirect effect through marine stratocumulus clouds

    Energy Technology Data Exchange (ETDEWEB)

    Kogan, Z.N.; Kogan, Y.L.; Lilly, D.K. [Univ. of Oklahoma, Norman, OK (United States)

    1996-04-01

    During the last decade much attention has been focused on anthropogenic aerosols and their radiative influence on the global climate. Charlson et al. and Penner et al. have demonstrated that tropospheric aerosols and particularly anthropogenic sulfate aerosols may significantly contribute to the radiative forcing exerting a cooling influence on climate (-1 to -2 W/m{sup 2}) which is comparable in magnitude to greenhouse forcing, but opposite in sign. Aerosol particles affect the earth`s radiative budget either directly by scattering and absorption of solar radiation by themselves or indirectly by altering the cloud radiative properties through changes in cloud microstructure. Marine stratocumulus cloud layers and their possible cooling influence on the atmosphere as a result of pollution are of special interest because of their high reflectivity, durability, and large global cover. We present an estimate of thet aerosol indirect effect, or, forcing due to anthropogenic sulfate aerosols.

  4. 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

  5. Aerosol-Forming Reactions of Glyoxal, Methylglyoxal and Amino Acids in Clouds

    Science.gov (United States)

    de Haan, D. O.; Smith, K. W.; Stroik, D. R.; Corrigan, A. L.; Lee, F. E.; Phan, J. T.; Conley, A. C.

    2008-12-01

    Glyoxal and methylglyoxal are two common aldehydes present in fog and cloud water. Amino acids are present in clouds at similar concentrations. Here we present bulk and aerosol mass spectroscopic data demonstrating that irreversible reactions between glyoxal and amino acids, triggered by droplet evaporation, produce N-derivatized imidazole compounds along with deeply colored Maillard reaction products. These reactions can occur in the dark and in the absence of oxidants. Reactions between methylglyoxal and amino acids produce analogous methylated products plus oligomers with masses up to m/z = 1000. These reactions, which go to completion on the 10-min-timescale of cloud processing, could be significant sources of secondary organic aerosol and humic-like substances (HULIS or brown carbon).

  6. The Pasadena Aerosol Characterization Observatory (PACO: chemical and physical analysis of the Western Los Angeles basin aerosol

    Directory of Open Access Journals (Sweden)

    S. P. Hersey

    2011-08-01

    in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode dominated by organics. Particulate NH4NO3 and (NH42SO4 appear to be NH3-limited in regimes I and II, but a significant excess of particulate NH4+ in the hot, dry regime III suggests less SO42− and the presence of either organic amines or NH4+-associated organic acids. C-ToF-AMS data were analyzed by Positive Matrix Factorization (PMF, which resolved three factors, corresponding to a hydrocarbon-like OA (HOA, semivolatile OOA (SV-OOA, and low-volatility OOA (LV-OOA. HOA appears to be a periodic plume source, while SV-OOA exhibits a strong diurnal pattern correlating with ozone. Peaks in SV-OOA concentration correspond to peaks in DMA number concentration and the appearance of a fine organic mode. LV-OOA appears to be an aged accumulation mode constituent that may be associated with aqueous-phase processing, correlating strongly with sulfate and representing the dominant background organic component. Periods characterized by high SV-OOA and LV-OOA were analyzed by filter analysis, revealing a complex mixture of species during periods dominated by SV-OOA and LV-OOA, with LV-OOA periods characterized by shorter-chain dicarboxylic acids (higher O:C ratio, as well as appreciable amounts of nitrate- and sulfate-substituted organics. Phthalic acid was ubiquitous in filter samples, suggesting that PAH photochemistry may be an important SOA pathway in Los Angeles. Aerosol composition was related to water uptake characteristics, and it is concluded that hygroscopicity is largely controlled by organic mass fraction (OMF. The hygroscopicity parameter κ averaged 0.31 ± 0.08, approaching 0.5 at low OMF and 0.1 at high OMF, with increasing OMF suppressing hygroscopic growth and increasing critical dry diameter for CCN activation

  7. 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.

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

    Science.gov (United States)

    Buzatu, Andrei; Dill, Harald G; Buzgar, Nicolae; Damian, Gheorghe; Maftei, Andreea Elena; Apopei, Andrei Ionuț

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Flight-based chemical characterization of biomass burning aerosols within two prescribed burn smoke plumes

    Directory of Open Access Journals (Sweden)

    K. A. Pratt

    2011-12-01

    Full Text Available Biomass burning represents a major global source of aerosols impacting direct radiative forcing and cloud properties. Thus, the goal of a number of current studies involves developing a better understanding of how the chemical composition and mixing state of biomass burning aerosols evolve during atmospheric aging processes. During the Ice in Clouds Experiment-Layer Clouds (ICE-L in the fall of 2007, smoke plumes from two small Wyoming Bureau of Land Management prescribed burns were measured by on-line aerosol instrumentation aboard a C-130 aircraft, providing a detailed chemical characterization of the particles. After ~2–4 min of aging, submicron smoke particles, produced primarily from sagebrush combustion, consisted predominantly of organics by mass, but were comprised primarily of internal mixtures of organic carbon, elemental carbon, potassium chloride, and potassium sulfate. Significantly, the fresh biomass burning particles contained minor mass fractions of nitrate and sulfate, suggesting that hygroscopic material is incorporated very near or at the point of emission. The mass fractions of ammonium, sulfate, and nitrate increased with aging up to ~81–88 min and resulted in acidic particles. Decreasing black carbon mass concentrations occurred due to dilution of the plume. Increases in the fraction of oxygenated organic carbon and the presence of dicarboxylic acids, in particular, were observed with aging. Cloud condensation nuclei measurements suggested all particles >100 nm were active at 0.5% water supersaturation in the smoke plumes, confirming the relatively high hygroscopicity of the freshly emitted particles. For immersion/condensation freezing, ice nuclei measurements at −32 °C suggested activation of ~0.03–0.07% of the particles with diameters greater than 500 nm.

  10. Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

    OpenAIRE

    Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

    1984-01-01

    Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds.

  11. 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......-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...... that the skin collagen architecture was altered, and electron microscopy showed that the DS-epi1-null fibrils have a larger diameter than the wild-type fibrils. The altered chondroitin/dermatan sulfate chains carried by decorin in skin are likely to affect collagen fibril formation and reduce the tensile...

  12. Esterification of fatty acids using sulfated zirconia and composites activated carbon/sulfated zirconia catalysts

    International Nuclear Information System (INIS)

    Brum, Sarah S.; Santos, Valeria C. dos; Destro, Priscila; Guerreiro, Mario Cesar

    2011-01-01

    In this work sulfated zirconia (SZr) and activated carbon/SZr composites produced by impregnation method with or without heating treatment step (CABC/SZr-I and CABC/SZr-I SC) and by the method of synthesis of SZr on the carbon (CABC/SZr-S) was used as catalysts in the esterification reactions of fatty acids. The SZr presented very active, conversions higher than 90% were obtained after 2 h of reaction. The activity of the composite CABC/SZr-I20%SC was up to 92%, however, this was directly related to time and temperature reactions. CABC/SZr-I and CABC/SZr-S were less active in esterification reactions, what could be attributed to its low acidity. (author)

  13. Evaluation of plant species for use in the control of acid sulfated soils in Paipa, Boyacá

    Directory of Open Access Journals (Sweden)

    Andrea Angélica Bernal Figueroa

    2014-07-01

    Full Text Available Acid sulfated soils are characterized by high amounts of iron and sulfur, which in presence of air are oxidized and form sulfuric horizons extremely acidic, generating environmental changes ranging from water pollution to problems associated with fertility and crop production, among others. This research was conducted in order to identify suitable plant species to control the acidity of these soils in the town of Paipa, Boyacá, Colombia. A completely randomized experimental design with 6 treatments and 3 replications was implemented in potting shed; there, the response of Beta vulgaris L. (forage beet, Brassica rapa L. (forage turnip and Raphanus sativus L. (forage radish on the acidity of sulfated acid soil, contrasted with a non-sulfated soil, was evaluated, after correction with liming. To assess the effects, pH and exchangeable acidity (H+ + Al+3 cmolc/kg were measured in the two types of soil before and after seeding ; the agronomic response of plants in each treatment was determined at the end of the growing season (120 days after seeding . On acid sulfated soils, species B. rapa, R. sativus and B. vulgaris along with the complementary use of liming as corrective induced a reduction in exchangeable acidity; B. rapa and R. sativus showed better growth potential and resistance, while B. vulgaris was affected in height and root diameter.

  14. 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.

  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

    1998-12-31

    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. 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.

  17. Wintertime water-soluble aerosol composition and particle water content in Fresno, California

    Science.gov (United States)

    Parworth, Caroline L.; Young, Dominique E.; Kim, Hwajin; Zhang, Xiaolu; Cappa, Christopher D.; Collier, Sonya; Zhang, Qi

    2017-03-01

    The composition and concentrations of water-soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle-into-liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m-3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol-phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E-AIM) thermodynamic prediction of inorganic particle water and κ-Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m-3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous-phase concentrations of ions calculated by using E-AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2).

  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,

  19. 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.

  20. Sulfate-reducing bacteria mediate thionation of diphenylarsinic acid under anaerobic conditions.

    Science.gov (United States)

    Guan, Ling; Shiiya, Ayaka; Hisatomi, Shihoko; Fujii, Kunihiko; Nonaka, Masanori; Harada, Naoki

    2015-02-01

    Diphenylarsinic acid (DPAA) is often found as a toxic intermediate metabolite of diphenylchloroarsine or diphenylcyanoarsine that were produced as chemical warfare agents and were buried in soil after the World Wars. In our previous study Guan et al. (J Hazard Mater 241-242:355-362, 2012), after application of sulfate and carbon sources, anaerobic transformation of DPAA in soil was enhanced with the production of diphenylthioarsinic acid (DPTAA) as a main metabolite. This study aimed to isolate and characterize anaerobic soil microorganisms responsible for the metabolism of DPAA. First, we obtained four microbial consortia capable of transforming DPAA to DPTAA at a high transformation rate of more than 80% after 4 weeks of incubation. Sequencing for the bacterial 16S rRNA gene clone libraries constructed from the consortia revealed that all the positive consortia contained Desulfotomaculum acetoxidans species. In contrast, the absence of dissimilatory sulfite reductase gene (dsrAB) which is unique to sulfate-reducing bacteria was confirmed in the negative consortia showing no DPAA reduction. Finally, strain DEA14 showing transformation of DPAA to DPTAA was isolated from one of the positive consortia. The isolate was assigned to D. acetoxidans based on the partial 16S rDNA sequence analysis. Thionation of DPAA was also carried out in a pure culture of a known sulfate-reducing bacterial strain, Desulfovibrio aerotolerans JCM 12613(T). These facts indicate that sulfate-reducing bacteria are microorganisms responsible for the transformation of DPAA to DPTAA under anaerobic conditions.

  1. Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2012-09-01

    Full Text Available Positive matrix factorization (PMF was applied to the merged high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS measurements to investigate the sources and evolution processes of submicron aerosols in New York City in summer 2009. This new approach is able to study the distribution of organic and inorganic species in different types of aerosols, the acidity of organic aerosol (OA factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrix resolved 8 factors. The hydrocarbon-like OA (HOA and cooking OA (COA factors contain negligible amounts of inorganic species. The two factors that are primarily ammonium sulfate (SO4-OA and ammonium nitrate (NO3-OA, respectively, are overall neutralized. Among all OA factors the organic fraction of SO4-OA shows the highest degree of oxidation (O/C = 0.69. Two semi-volatile oxygenated OA (OOA factors, i.e., a less oxidized (LO-OOA and a more oxidized (MO-OOA, were also identified. MO-OOA represents local photochemical products with a diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO and Ox(= O3 + NO2. The NO+/NO2+ ion ratio in MO-OOA is much higher than that in NO3-OA and in pure ammonium nitrate, indicating the formation of organic nitrates. The nitrogen-enriched OA (NOA factor contains ~25% of acidic inorganic salts, suggesting the formation of secondary OA via acid-base reactions of amines. The size distributions of OA factors derived from the size-resolved mass spectra show distinct diurnal evolving behaviors but overall a progressing evolution from smaller to larger particle mode as the oxidation degree of OA increases. Our results demonstrate that PMF analysis of the unified aerosol mass spectral matrix which contains both

  2. Anthropogenic Influence on Secondary Aerosol Formation and Total Water-Soluble Carbon on Atmospheric Particles

    Science.gov (United States)

    Gioda, Adriana; Mateus, Vinicius; Monteiro, Isabela; Taira, Fabio; Esteves, Veronica; Saint'Pierre, Tatiana

    2013-04-01

    On a global scale, the atmosphere is an important source of nutrients, as well as pollutants, because of its interfaces with soil and water. Important compounds in the gaseous phase are in both organic and inorganic forms, such as organic acids, nitrogen, sulfur and chloride. In spite of the species in gas form, a huge number of process, anthropogenic and natural, are able to form aerosols, which may be transported over long distances. Sulfates e nitrates are responsible for rain acidity; they may also increase the solubility of organic compounds and metals making them more bioavailable, and also can act as cloud condensation nuclei (CCN). Aerosol samples (PM2.5) were collected in a rural and industrial area in Rio de Janeiro, Brazil, in order to quantify chemical species and evaluate anthropogenic influences in secondary aerosol formation and organic compounds. Samples were collected during 24 h every six days using a high-volume sampler from August 2010 to July 2011. The aerosol mass was determined by Gravimetry. The water-soluble ionic composition (WSIC) was obtained by Ion Chromatography in order to determine the major anions (NO3-, SO4= and Cl-); total water-soluble carbon (TWSC) was determined by a TOC analyzer. The average aerosol (PM2.5) concentrations ranged from 1 to 43 ug/m3 in the industrial site and from 4 to 35 ug/m3 in the rural area. Regarding anions, the highest concentrations were measured for SO42- (10.6 μg/m3-12.6 μg/m3); where the lowest value was found in the rural site and the highest in the industrial. The concentrations for NO3- and Cl- ranged from 4.2 μg/m3 to 9.3 μg/m3 and 3.1 μg/m3 to 6.4 μg /m3, respectively. Sulfate was the major species and, like nitrate, it is related to photooxidation in the atmosphere. Interestingly sulfate concentrations were higher during the dry period and could be related to photochemistry activity. The correlations between nitrate and non-sea-salt sulfate were weak, suggesting different sources for these

  3. 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.

  4. Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

    Science.gov (United States)

    Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

    1984-01-01

    Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds. PMID:16346592

  5. Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

    Directory of Open Access Journals (Sweden)

    Nurgul Balci

    2017-08-01

    Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

  6. Measurement of chemical leaching potential of sulfate from landfill disposed sulfate containing wastes.

    Science.gov (United States)

    Sun, Wenjie; Barlaz, Morton A

    2015-02-01

    A number of sulfate-containing wastes are disposed in municipal solid wastes (MSW) landfills including residues from coal, wood, and MSW combustion, and construction and demolition (C&D) waste. Under anaerobic conditions that dominate landfills, the sulfate can be reduced to hydrogen sulfide which is problematic for several reasons including its low odor threshold, toxicity, and corrosive nature. The overall objective of this study was to evaluate existing protocols for the quantification of total leachable sulfate from solid samples and to compare their effectiveness and efficiency with a new protocol described in this study. Methods compared include two existing acid extraction protocols commonly used in the U.S., a pH neutral protocol that requires multiple changes of the leaching solution, and a new acid extraction method. The new acid extraction method was shown to be simple and effective to measure the leaching potential of sulfate from a range of landfill disposed sulfate-containing wastes. However, the acid extraction methods do not distinguish between sulfate and other forms of sulfur and are thus most useful when sulfate is the only form of sulfur present. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Aerosol activation and cloud processing in the global aerosol-climate model ECHAM5-HAM

    Directory of Open Access Journals (Sweden)

    G. J. Roelofs

    2006-01-01

    Full Text Available A parameterization for cloud processing is presented that calculates activation of aerosol particles to cloud drops, cloud drop size, and pH-dependent aqueous phase sulfur chemistry. The parameterization is implemented in the global aerosol-climate model ECHAM5-HAM. The cloud processing parameterization uses updraft speed, temperature, and aerosol size and chemical parameters simulated by ECHAM5-HAM to estimate the maximum supersaturation at the cloud base, and subsequently the cloud drop number concentration (CDNC due to activation. In-cloud sulfate production occurs through oxidation of dissolved SO2 by ozone and hydrogen peroxide. The model simulates realistic distributions for annually averaged CDNC although it is underestimated especially in remote marine regions. On average, CDNC is dominated by cloud droplets growing on particles from the accumulation mode, with smaller contributions from the Aitken and coarse modes. The simulations indicate that in-cloud sulfate production is a potentially important source of accumulation mode sized cloud condensation nuclei, due to chemical growth of activated Aitken particles and to enhanced coalescence of processed particles. The strength of this source depends on the distribution of produced sulfate over the activated modes. This distribution is affected by uncertainties in many parameters that play a direct role in particle activation, such as the updraft velocity, the aerosol chemical composition and the organic solubility, and the simulated CDNC is found to be relatively sensitive to these uncertainties.

  8. Sulfate Aerosol in the Arctic: Source Attribution and Radiative Forcing

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yang [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland WA USA; Wang, Hailong [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland WA USA; Smith, Steven J. [Joint Global Change Research Institute, Pacific Northwest National Laboratory, College Park MD USA; Easter, Richard C. [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland WA USA; Rasch, Philip J. [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland WA USA

    2018-02-08

    Source attributions of Arctic sulfate and its direct radiative effect for 2010–2014 are quantified in this study using the Community Earth System Model (CESM) equipped with an explicit sulfur source-tagging technique. Regions that have high emissions and/or are near/within the Arctic present relatively large contributions to Arctic sulfate burden, with the largest contribution from sources in East Asia (27%). East Asia and South Asia together have the largest contributions to Arctic sulfate concentrations at 9–12 km, whereas sources within or near the Arctic account largely below 2 km. For remote sources with strong emissions, their contributions to Arctic sulfate burden are primarily driven by meteorology, while contributions of sources within or near the Arctic are dominated by their emission strength. The sulfate direct radiative effect (DRE) is –0.080 W m-2 at the Arctic surface, offsetting the net warming effect from the combination of in-snow heating and DRE cooling from black carbon. East Asia, Arctic local and Russia/Belarus/Ukraine sources contribute –0.017, –0.016 and –0.014 W m-2, respectively, to Arctic sulfate DRE. A 20% reduction in anthropogenic SO2 emissions leads to a net increase of +0.013 W m-2 forcing at the Arctic surface. These results indicate that a joint reduction in BC emissions could prevent possible Arctic warming from future reductions in SO2 emissions. Sulfate DRE efficiency calculations suggest that short transport pathways together with meteorology favoring long sulfate lifetimes make certain sources more efficient in influencing the Arctic sulfate DRE.

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

    OpenAIRE

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

    2016-01-01

    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-1-piperidinyloxy (TEMPO) and bis(acetoxy)iodobenzene (BAIB). This is...

  10. Aerosol characterization study using multi-spectrum remote sensing measurement techniques.

    Energy Technology Data Exchange (ETDEWEB)

    Glen, Crystal Chanea; Sanchez, Andres L.; Lucero, Gabriel Anthony; Schmitt, Randal L.; Johnson, Mark S.; Tezak, Matthew S; Servantes, Brandon Lee

    2013-09-01

    A unique aerosol flow chamber coupled with a bistatic LIDAR system was implemented to measure the optical scattering cross sections and depolarization ratio of common atmospheric particulates. Each of seven particle types (ammonium sulfate, ammonium nitrate, sodium chloride, potassium chloride, black carbon and Arizona road dust) was aged by three anthropogenically relevant mechanisms: 1. Sulfuric acid deposition, 2. Toluene ozonolysis reactions, and 3. m-Xylene ozonolysis reactions. The results of pure particle scattering properties were compared with their aged equivalents. Results show that as most particles age under industrial plume conditions, their scattering cross sections are similar to pure black carbon, which has significant impacts to our understanding of aerosol impacts on climate. In addition, evidence emerges that suggest chloride-containing aerosols are chemically altered during the organic aging process. Here we present the direct measured scattering cross section and depolarization ratios for pure and aged atmospheric particulates.

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

    Directory of Open Access Journals (Sweden)

    P. S. Bhattacharjee

    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.

  12. Organic Aerosols as Cloud Condensation Nuclei

    Science.gov (United States)

    Hudson, J. G.

    2002-05-01

    The large organic component of the atmospheric aerosol contributes to both natural and anthropogenic cloud condensation nuclei (CCN). Moreover, some organic substances may reduce droplet surface tension (Facchini et al. 1999), while others may be partially soluble (Laaksonen et al. 1998), and others may inhibit water condensation. The interaction of organics with water need to be understood in order to better understand the indirect aerosol effect. Therefore, laboratory CCN spectral measurements of organic aerosols are presented. These are measurements of the critical supersaturation (Sc), the supersaturation needed to produce an activated cloud droplet, as a function of the size of the organic particles. Substances include sodium lauryl (dodecyl) sulfate, oxalic, adipic, pinonic, hexadecanedioic, glutaric, stearic, succinic, phthalic, and benzoic acids. These size-Sc relationships are compared with theoretical and measured size-Sc relationships of common inorganic compounds (e.g., NaCl, KI, ammonium and calcium sulfate). Unlike most inorganics some organics display variations in solubility per unit mass as a function of particle size. Those showing relatively greater solubility at smaller sizes may be attributable to surface tension reduction, which is greater for less water dilution, as is the case for smaller particles, which are less diluted at the critical sizes. This was the case for sodium dodecyl sulfate, which does reduce surface tension. Relatively greater solubility for larger particles may be caused by greater dissolution at the higher dilutions that occur with larger particles; this is partial solubility. Measurements are also presented of internal mixtures of various organic and inorganic substances. These measurements were done with two CCN spectrometers (Hudson 1989) operating simultaneously. These two instruments usually displayed similar results in spite of the fact that they have different flow rates and supersaturation profiles. The degree of

  13. A global off-line model of size-resolved aerosol microphysics: I. Model development and prediction of aerosol properties

    Directory of Open Access Journals (Sweden)

    D. V. Spracklen

    2005-01-01

    Full Text Available A GLObal Model of Aerosol Processes (GLOMAP has been developed as an extension to the TOMCAT 3-D Eulerian off-line chemical transport model. GLOMAP simulates the evolution of the global aerosol size distribution using a sectional two-moment scheme and includes the processes of aerosol nucleation, condensation, growth, coagulation, wet and dry deposition and cloud processing. We describe the results of a global simulation of sulfuric acid and sea spray aerosol. The model captures features of the aerosol size distribution that are well established from observations in the marine boundary layer and free troposphere. Modelled condensation nuclei (CN>3nm vary between about 250–500 cm-3 in remote marine boundary layer regions and are generally in good agreement with observations. Modelled continental CN concentrations are lower than observed, which may be due to lack of some primary aerosol sources or the neglect of nucleation mechanisms other than binary homogeneous nucleation of sulfuric acid-water particles. Remote marine CN concentrations increase to around 2000–10 000 cm (at standard temperature and pressure in the upper troposphere, which agrees with typical observed vertical profiles. Cloud condensation nuclei (CCN at 0.2% supersaturation vary between about 1000 cm-3 in polluted regions and between 10 and 500 cm-3 in the remote marine boundary layer. New particle formation through sulfuric acid-water binary nucleation occurs predominantly in the upper troposphere, but the model results show that these particles contribute greatly to aerosol concentrations in the marine boundary layer. For this sulfur-sea salt system it is estimated that sea spray emissions account for only ~10% of CCN in the tropical marine boundary layer, but between 20 and 75% in the mid-latitude Southern Ocean. In a run with only natural sulfate and sea salt emissions the global mean surface CN concentration is more than 60% of that from a run with 1985 anthropogenic

  14. 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.

  15. Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

    Science.gov (United States)

    Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

    2017-08-10

    A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

  16. Decontamination of acid mine water from Ronneburg/Thueringen which is high in sulfates and metals using sulfate-reducing bacteria. Final report of the preliminary phase

    International Nuclear Information System (INIS)

    Hard, B.; Friedrich, S.

    1995-01-01

    The mining in Eastern Europe, particularly in East-Germany, is a major source of pollution to the surrounding areas of the mines. With the end of the cold war the demand for uranium has drastically declined. Many of the pits have therefore been closed down or are in the process of closure such as the uranium mine in Ronneburg in Thueringen. One major problem is the safe-making of the pits and dumps as they are highly radioactive through naturally occurring uranium and other radioactive elements. Because of the leaching process through bacteria, drainage water is very acidic, with pH-values between 1-2. The water is very rich in magnesium, iron and aluminium sulfate. Here the application of a microbial process to decontaminate acid mine drainage was investigated. Decontamination of the water includes: - Increase in pH - decrease in sulfate concentrations - minimization of the metal and radionuclide load. Sulfate-reducing bacteria seem suitable for this process. In order for such a microbial process to be economically viable a cheap and widely available electron donar has to be used eg. methanol. The work carried out reports on the isolation, characterization and physiology of sulfate-reducing methylotrophic bacteria and their suitability for a decontamination process of sulfuric acid uranium mine water. (orig.) [de

  17. 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.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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.

  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. Interactions of aerosols (ammonium sulfate, ammonium nitrate and ammonium chloride) and of gases (HCl, HNO 3) with fogwater

    Science.gov (United States)

    Ruprecht, Heidi; Sigg, Laura

    The concentrations of aerosols (NH 4NO 3, (NH 4) 2SO 4 and NH 4Cl) and of gases (HCl (g), HNO 3(g), NH 3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl (g) and HNO 3(g) are observed. NH 4Cl and NH 4NO 3 aerosols represent a major fraction of the Cl - and NO 3- aerosols (fogwater and are released again after fog dissipation.

  1. Changes of fatty acid aerosol hygroscopicity induced by ozonolysis under humid conditions

    Directory of Open Access Journals (Sweden)

    O. Vesna

    2008-08-01

    Full Text Available Unsaturated fatty acids are important constituents of the organic fraction of atmospheric aerosols originating from biogenic or combustion sources. Oxidative processing of these may change their interaction with water and thus affect their effect on climate. The ozonolysis of oleic and arachidonic acid aerosol particles was studied under humid conditions in a flow reactor at ozone exposures close to atmospheric levels, at concentrations between 0.5 and 2 ppm. While oleic acid is a widely used proxy for such studies, arachidonic acid represents polyunsaturated fatty acids, which may decompose into hygroscopic products. The hygroscopic (diameter growth factor at 93% relative humidity (RH of the oxidized arachidonic particles increased up to 1.09 with increasing RH during the ozonolysis. In contrast, the growth factor of oleic acid was very low (1.03 at 93% RH and was almost invariant to the ozonolysis conditions, so that oleic acid is not a good model to observe oxidation induced changes of hygroscopicity under atmospheric conditions. We show for arachidonic acid particles that the hygroscopic changes induced by humidity during ozonolysis are accompanied by about a doubling of the ratio of carboxylic acid protons to aliphatic protons. We suggest that, under humid conditions, the reaction of water with the Criegee intermediates might open a pathway for the formation of smaller acids that lead to more significant changes in hygroscopicity. Thus the effect of water to provide a competing pathway during ozonolysis observed in this study should be motivation to include water, which is ubiquitously present in and around atmospheric particles, in future studies related to aerosol particle aging.

  2. Aerosol composition, chemistry, and source characterization during the 2008 VOCALS Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.; Springston, S.; Jayne, J.; Wang, J.; Senum, G.; Hubbe, J.; Alexander, L.; Brioude, J.; Spak, S.; Mena-Carrasco, M.; Kleinman, L.; Daum, P.

    2010-03-15

    Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+ rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only {approx}0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on sea-salt aerosols, responsible for the Cl- deficit. Dust particles appeared to play a minor role, judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations were substantial ({approx}0.5 - {approx}3 {micro}g/m3) with a strong gradient (highest near the shore), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., {le} 40 parts per trillion and <0.05 {micro}g/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4- aerosols. However, compared to observations, model

  3. 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 <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea 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

  4. BASE COMPOSITION OF THE DEOXYRIBONUCLEIC ACID OF SULFATE-REDUCING BACTERIA.

    Science.gov (United States)

    SIGAL, N; SENEZ, J C; LEGALL, J; SEBALD, M

    1963-06-01

    Sigal, Nicole (Laboratoire de Chimie Bactérienne du CNRS, Marseille, France), Jacques C. Senez, Jean Le Gall, and Madeleine Sebald. Base composition of the deoxyribonucleic acid of sulfate-reducing bacteria. J. Bacteriol. 85:1315-1318. 1963-The deoxyribonucleic acid constitution of several strains of sulfate-reducing bacteria has been analytically determined. The results of these studies show that this group of microorganisms includes at least four subgroups characterized by significantly different values of the adenine plus thymine to guanine plus cytosine ratio. The nonsporulated forms with polar flagellation, containing both cytochrome c(3) and desulfoviridin, are divided into two subgroups. One includes the fresh-water, nonhalophilic strains with base ratio from 0.54 to 0.59, and the other includes the halophilic or halotolerant strains with base ratio from 0.74 to 0.77. The sporulated, peritrichous strains without cytochrome and desulfoviridin ("nigrificans" and "orientis") are distinct from the above two types and differ from each other, having base ratios of 1.20 and 1.43, respectively.

  5. Sensitivity studies of different aerosol indirect effects in mixed-phase clouds

    Science.gov (United States)

    Lohmann, U.; Hoose, C.

    2009-11-01

    Aerosols affect the climate system by changing cloud characteristics. Using the global climate model ECHAM5-HAM, we investigate different aerosol effects on mixed-phase clouds: The glaciation effect, which refers to a more frequent glaciation due to anthropogenic aerosols, versus the de-activation effect, which suggests that ice nuclei become less effective because of an anthropogenic sulfate coating. The glaciation effect can partly offset the indirect aerosol effect on warm clouds and thus causes the total anthropogenic aerosol effect to be smaller. It is investigated by varying the parameterization for the Bergeron-Findeisen process and the threshold coating thickness of sulfate (SO4-crit), which is required to convert an externally mixed aerosol particle into an internally mixed particle. Differences in the net radiation at the top-of-the-atmosphere due to anthropogenic aerosols between the different sensitivity studies amount up to 0.5 W m-2. This suggests that the investigated mixed-phase processes have a major effect on the total anthropogenic aerosol effect.

  6. Tethered balloon-borne aerosol measurements: seasonal and vertical variations of aerosol constituents over Syowa Station, Antarctica

    Directory of Open Access Journals (Sweden)

    K. Hara

    2013-09-01

    Full Text Available Tethered balloon-borne aerosol measurements were conducted at Syowa Station, Antarctica, during the 46th Japanese Antarctic expedition (2005–2006. Direct aerosol sampling was operated from near the surface to the lower free troposphere (approximately 2500 m using a balloon-borne aerosol impactor. Individual aerosol particles were analyzed using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer. Seasonal and vertical features of aerosol constituents and their mixing states were investigated. Results show that sulfate particles were predominant in the boundary layer and lower free troposphere in summer, whereas sea-salt particles were predominant during winter through spring. Minerals, MgSO4, and sulfate containing K were identified as minor aerosol constituents in both boundary layer and free troposphere over Syowa Station. Although sea-salt particles were predominant during winter through spring, the relative abundance of sulfate particles increased in the boundary layer when air masses fell from the free troposphere over the Antarctic coast and continent. Sea-salt particles were modified considerably through heterogeneous reactions with SO42− CH3SO3− and their precursors during summer, and were modified slightly through heterogeneous reactions with NO3− and its precursors. During winter through spring, sea-salt modification was insignificant, particularly in the cases of high relative abundance of sea-salt particles and higher number concentrations. In August, NO3− and its precursors contributed greatly to sea-salt modification over Syowa Station. Because of the occurrence of sea-salt fractionation on sea ice, Mg-rich sea-salt particles were identified during the months of April through November. In contrast, Mg-free sea-salt particles and slightly Mg-rich sea-salt particles coexisted in the lower troposphere during summer. Thereby, Mg separation can proceed by sea-salt fractionation during summer in

  7. Aerosol concentrations and composition in the North Pacific marine boundary layer

    Science.gov (United States)

    Choi, Yongjoo; Rhee, Tae Siek; Collett, Jeffrey L.; Park, Taehyun; Park, Seung-Myung; Seo, Beom-Keun; Park, Gyutae; Park, Keyhong; Lee, Taehyoung

    2017-12-01

    Ship-borne measurements of inorganic and organic aerosols, including methanesulfonic acid (MSA), were conducted over the Northern Pacific using a High Resolution Time of Flight Aerosol Mass Spectrometer (AMS). This study, conducted aboard the Korean ice breaker R/V Araon, was part of the SHIP-borne Pole-to-Pole Observations (SHIPPO) project. Based on air mass source region, the cruise track could be divided into five sections. Overall, the South Asia and Northern Japan ship transects showed higher aerosol concentrations due to continental pollution and biomass burning sources, respectively. In all five regions, the average mass concentrations of sulfate and organic aerosols (OA) were much higher than concentrations of nitrate and ammonium. Positive matrix factorization (PMF) analysis distinguished two organic aerosol factors as hydrocarbon-like and oxidized OA (HOA and OOA). HOA peaked in South Asia under the influence of anthropogenic pollution source areas, such as China and Korea, and generally decreased with increasing latitude across the full study region. OOA concentrations peaked in Northern Japan near the Tsugaru Strait and appear to reflect fine particle contributions from biomass burning. The mean HOA concentration in the clean marine area (Aleutian Island to Siberia) was 0.06 μg/m3 and comprised approximately 8% of the OA mass fraction. The highest MSA concentrations peaked in the Aleutian Islands at nearly 15 μg/m3, suggesting influence from higher dimethyl sulfide (DMS) emissions resulting from biological nutrient uptake during summer. The MSA/sulfate ratio, an indicator of the relative fine particle contributions of DMS and anthropogenic sources, revealed a sharp gradient as the ship approached the clean marine areas where the dominance of DMS increased. The patterns in OOA, HOA, and MSA concentrations found in this study provide a better understanding of the characteristics of inorganic and organic aerosols in the Northern Pacific Ocean.

  8. Observations of linear dependence between sulfate and nitrate in atmospheric particles

    Science.gov (United States)

    Kong, Lingdong; Yang, Yiwei; Zhang, Shuanqin; Zhao, Xi; Du, Huanhuan; Fu, Hongbo; Zhang, Shicheng; Cheng, Tiantao; Yang, Xin; Chen, Jianmin; Wu, Dui; Shen, Jiandong; Hong, Shengmao; Jiao, Li

    2014-01-01

    Hourly measurements of water-soluble inorganic ionic species in ambient atmospheric particles were conducted at Shanghai, Hangzhou, and Guangzhou sampling sites in China during the period of 2009-2011. The relation between sulfate and nitrate in particulate matter (PM10 and PM2.5) was examined based on these measurements. Results showed that the mass fraction of sulfate was strongly negatively correlated with that of nitrate in atmospheric particles on most of the sampling days, especially when sulfate and nitrate made up the vast majority of the total soluble anions and cations (Na+, K+, Ca2+, and Mg2+) made a small contribution to the total water-soluble ions, revealing that the formation mechanisms of sulfate and nitrate in the atmosphere are highly correlated, and there exists a significant negative correlation trend between sulfate and nitrate mass fractions in the atmospheric particles. We found that local meteorological conditions presented opposite influences on the mass fractions of sulfate and nitrate. Further analysis indicated that the two mass fractions were modulated by the neutralizing level of atmospheric aerosols, and the negative correlation could be found in acidic atmospheric particles. Strong negative correlation was usually observed on clear days, hazy days, foggy days, and respirable particulate air pollution days, whereas poor negative correlation was often observed during cloud, rain, snow, dust storm, and suspended dust events. The results can help to better understand the formation mechanisms of atmospheric sulfate and nitrate during air pollution episodes and to better explain field results of atmospheric chemistry concerning sulfate and nitrate.

  9. Advances in biotreatment of acid mine drainage and biorecovery of metals: 2. Membrane bioreactor system for sulfate reduction.

    Science.gov (United States)

    Tabak, Henry H; Govind, Rakesh

    2003-12-01

    Several biotreatmemt techniques for sulfate conversion by the sulfate reducing bacteria (SRB) have been proposed in the past, however few of them have been practically applied to treat sulfate containing acid mine drainage (AMD). This research deals with development of an innovative polypropylene hollow fiber membrane bioreactor system for the treatment of acid mine water from the Berkeley Pit, Butte, MT, using hydrogen consuming SRB biofilms. The advantages of using the membrane bioreactor over the conventional tall liquid phase sparged gas bioreactor systems are: large microporous membrane surface to the liquid phase; formation of hydrogen sulfide outside the membrane, preventing the mixing with the pressurized hydrogen gas inside the membrane; no requirement of gas recycle compressor; membrane surface is suitable for immobilization of active SRB, resulting in the formation of biofilms, thus preventing washout problems associated with suspended culture reactors; and lower operating costs in membrane bioreactors, eliminating gas recompression and gas recycle costs. Information is provided on sulfate reduction rate studies and on biokinetic tests with suspended SRB in anaerobic digester sludge and sediment master culture reactors and with SRB biofilms in bench-scale SRB membrane bioreactors. Biokinetic parameters have been determined using biokinetic models for the master culture and membrane bioreactor systems. Data are presented on the effect of acid mine water sulfate loading at 25, 50, 75 and 100 ml/min in scale-up SRB membrane units, under varied temperatures (25, 35 and 40 degrees C) to determine and optimize sulfate conversions for an effective AMD biotreatment. Pilot-scale studies have generated data on the effect of flow rates of acid mine water (MGD) and varied inlet sulfate concentrations in the influents on the resultant outlet sulfate concentration in the effluents and on the number of SRB membrane modules needed for the desired sulfate conversion in

  10. Stress corrosion cracking of Ni-Fe-Cr alloys in acid sulfate environments relevant to CANDU steam generators

    Energy Technology Data Exchange (ETDEWEB)

    Persaud, S.Y.; Carcea, A.G., E-mail: suraj.persaud@mail.utoronto.ca [Univ. of Toronto, Toronto, ON (Canada); Huang, J.; Korinek, A.; Botton, G.A. [McMaster Univ., Hamilton, ON (Canada); Newman, R.C. [Univ. of Toronto, Toronto, ON (Canada)

    2014-07-01

    Ni-Fe-Cr alloys used in nuclear plants have been found susceptible to stress corrosion cracking (SCC) in acid sulfate environments. Electrochemical measurements and SCC tests were done using Ni, Alloy 600, and Alloy 800 in acid sulfate solutions at 315 {sup o}C. Electrochemical measurements suggested that sulfate is a particularly aggressive anion in mixed chloride systems. Cracks with lengths in excess of 300 μm were present on stressed Alloy 800 samples after 60 hours. High resolution analytical electron microscopy was used to extract a crack tip from an Alloy 800 sample and draw final conclusions with respect to the mechanism of SCC. (author)

  11. Vacuum FTIR Observation on the Dynamic Hygroscopicity of Aerosols under Pulsed Relative Humidity.

    Science.gov (United States)

    Leng, Chun-Bo; Pang, Shu-Feng; Zhang, Yun; Cai, Chen; Liu, Yong; Zhang, Yun-Hong

    2015-08-04

    A novel approach based on a combination of a pulse RH controlling system and a rapid scan vacuum FTIR spectrometer (PRHCS-RSVFTIR) was utilized to investigate dynamic hygroscopicity of two atmospheric aerosols: ammonium sulfate ((NH4)2SO4) and magnesium sulfate (MgSO4). In this approach, rapid-scan infrared spectra of water vapor and aerosols were obtained to determine relative humidity (RH) in sample cell and hygroscopic property of aerosols with a subsecond time resolution. Heterogeneous nucleation rates of (NH4)2SO4 were, for the first time, measured under low RH conditions (nucleation kinetics of liquid aerosols.

  12. Size Distributions and Formation Pathways of Organic and Inorganic Constituents in Spring Aerosols from Okinawa Island in the Western North Pacific Rim: An Outflow Region of Asian Dusts

    Science.gov (United States)

    Deshmukh, D. K.; Lazaar, M.; Kawamura, K.; Kunwar, B.; Tachibana, E.; Boreddy, S. K. R.

    2015-12-01

    Size-segregated aerosols (9-stages) were collected at Okinawa Island in the western North Pacific Rim in spring 2008. The samples were analyzed for diacids (C2-C12), ω-oxoacids (ωC2-ωC9), a-dicarbonyls (C2-C3), organic carbon (OC), water-soluble OC (WSOC) and major ions to understand the sources and atmospheric processes in the outflow region of Asian pollutants. The molecular distribution of diacids showed the predominance of oxalic acid (C2) followed by malonic and succinic acids in all the size-segregated aerosols. ω-Oxoacids showed the predominance of glyoxylic acid (ωC2) whereas glyoxal (Gly) was more abundant than methylglyoxal in all the sizes. The abundant presence of sulfate as well as phthalic and adipic acids in Okinawa aerosols suggested a significant contribution of anthropogenic sources in East Asia via long-range atmospheric transport. Diacids (C2-C5), ωC2 and Gly as well as WSOC and OC peaked at 0.65-1.1 µm in fine mode whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at 3.3-4.7 µm in coarse mode. Sulfate and ammonium are enriched in fine mode whereas sodium and chloride are in coarse mode. An important mechanism for the formation of these organic species in Okinawa aerosols is probably gas phase oxidation of VOCs and subsequent in-cloud processing during long-range transport. Their characteristics size distribution implies that fine particles enriched with these organic and inorganic species could act as CCN to develop the cloud cover over the western North Pacific. The major peak of C9 and ωC9 on coarse mode suggest that they are produced by photooxidation of unsaturated fatty acids mainly derived from phytoplankton via heterogeneous reactions on sea spray particles. This study demonstrates that anthropogenic aerosols emitted from East Asia have significant influence on the compositions of organic and inorganic aerosols in the western North Pacific Rim.

  13. Hydrometallurgical process for recovering iron sulfate and zinc sulfate from baghouse dust

    Science.gov (United States)

    Zaromb, Solomon; Lawson, Daniel B.

    1994-01-01

    A process for recovering zinc/rich and iron-rich fractions from the baghouse dust that is generated in various metallurgical operations, especially in steel-making and other iron-making plants, comprises the steps of leaching the dust by hot concentrated sulfuric acid so as to generate dissolved zinc sulfate and a precipitate of iron sulfate, separating the precipitate from the acid by filtration and washing with a volatile liquid, such as methanol or acetone, and collecting the filtered acid and the washings into a filtrate fraction. The volatile liquid may be recovered distillation, and the zinc may be removed from the filtrate by alternative methods, one of which involves addition of a sufficient amount of water to precipitate hydrated zinc sulfate at 10.degree. C., separation of the precipitate from sulfuric acid by filtration, and evaporation of water to regenerate concentrated sulfuric acid. The recovery of iron may also be effected in alternative ways, one of which involves roasting the ferric sulfate to yield ferric oxide and sulfur trioxide, which can be reconverted to concentrated sulfuric acid by hydration. The overall process should not generate any significant waste stream.

  14. Climate effects of anthropogenic sulfate: Simulations from a coupled chemistry/climate model

    International Nuclear Information System (INIS)

    Chuang, C.C.; Penner, J.E.; Taylor, K.E.; Walton, J.J.

    1993-09-01

    In this paper, we use a more comprehensive approach by coupling a climate model with a 3-D global chemistry model to investigate the forcing by anthropogenic aerosol sulfate. The chemistry model treats the global-scale transport, transformation, and removal of SO 2 , DMS and H 2 SO 4 species in the atmosphere. The mass concentration of anthropogenic sulfate from fossil fuel combustion and biomass burning is calculated in the chemistry model and provided to the climate model where it affects the shortwave radiation. We also investigate the effect, with cloud nucleation parameterized in terms of local aerosol number, sulfate mass concentration and updraft velocity. Our simulations indicate that anthropogenic sulfate may result in important increases in reflected solar radiation, which would mask locally the radiative forcing from increased greenhouse gases. Uncertainties in these results will be discussed

  15. 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 (H 2 SO 4 ) 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

  16. Do atmospheric aerosols form glasses?

    Directory of Open Access Journals (Sweden)

    D. A. Pedernera

    2008-09-01

    Full Text Available A new process is presented by which water soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, Tg, homogeneous ice nucleation temperatures, Thom, and ice melting temperatures, Tm, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulfate and mixtures of dicarboxylic acids (M5, of dicarboxylic acids and ammonium sulfate (M5AS, of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show Tg values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K. To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher Tg of their respective solutions at a given water activity. To a lesser extent, Tg also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger (≳150 g mol−1 and

  17. Impacts of Four SO2 Oxidation Pathways on Wintertime Sulfate Concentrations

    Science.gov (United States)

    Sarwar, G.; Fahey, K.; Zhang, Y.; Kang, D.; Mathur, R.; Xing, J.; Wei, C.; Cheng, Y.

    2017-12-01

    Air quality models tend to under-estimate winter-time sulfate concentrations compared to observed data. Such under-estimations are particularly acute in China where very high concentrations of sulfate have been measured. Sulfate is produced by oxidation of sulfur dioxide (SO2) in gas-phase by hydroxyl radical and in aqueous-phase by hydrogen peroxide, ozone, etc. and most air quality models employ such typical reactions. Several additional SO2 oxidation pathways have recently been proposed. Heterogeneous reaction on dust has been suggested to be an important sink for SO2. Oxidation of SO2 on fine particles in presence of nitrogen dioxide (NO2) and ammonia (NH3) at high relative humidity has been implicated for sulfate formation in Chinese haze and London fog. Reactive nitrogen chemistry in aerosol water has also been suggested to produce winter-time sulfate in China. Specifically, high aerosol water can trap SO2 which can be subsequently oxidized by NO2 to form sulfate. Aqueous-phase (in-cloud) oxidation of SO2 by NO2 can also produce sulfate. Here, we use the hemispheric Community Multiscale Air Quality (CMAQ) modeling system to examine the potential impacts of these SO2 oxidation pathways on sulfate formation. We use anthropogenic emissions from the Emissions Database for Global Atmospheric Research and biogenic emissions from Global Emissions InitiAtive. We performed simulations without and with these SO2 oxidation pathways for October-December of 2014 using meteorological fields obtained from the Weather Research and Forecasting model. The standard CMAQ model contains one gas-phase chemical reaction and five aqueous-phase chemical reactions for SO2 oxidation. We implement four additional SO2 oxidation pathways into the CMAQ model. Our preliminary results suggest that the dust chemistry enhances mean sulfate over parts of China and Middle-East, the in-cloud SO2 oxidation by NO2 enhances sulfate over parts of western Europe, oxidation of SO2 by NO2 and NH3 on

  18. Aged organic aerosol in the Eastern Mediterranean: the Finokalia Aerosol Measurement Experiment – 2008

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2010-05-01

    Full Text Available Aged organic aerosol (OA was measured at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2008 (FAME-2008, which was part of the EUCAARI intensive campaign of May 2008. The site at Finokalia is influenced by air masses from different source regions, including long-range transport of pollution from continental Europe. A quadrupole aerosol mass spectrometer (Q-AMS was employed to measure the size-resolved chemical composition of non-refractory submicron aerosol (NR-PM1, and to estimate the extent of oxidation of the organic aerosol. Factor analysis was used to gain insights into the processes and sources affecting the OA composition. The particles were internally mixed and liquid. The largest fraction of the dry NR-PM1 sampled was ammonium sulfate and ammonium bisulfate, followed by organics and a small amount of nitrate. The variability in OA composition could be explained with two factors of oxygenated organic aerosol (OOA with differing extents of oxidation but similar volatility. Hydrocarbon-like organic aerosol (HOA was not detected. There was no statistically significant diurnal variation in the bulk composition of NR-PM1 such as total sulfate or total organic aerosol concentrations. However, the OA composition exhibited statistically significant diurnal variation with more oxidized OA in the afternoon. The organic aerosol was highly oxidized, regardless of the source region. Total OA concentrations also varied little with source region, suggesting that local sources had only a small effect on OA concentrations measured at Finokalia. The aerosol was transported for about one day before arriving at the site, corresponding to an OH exposure of approximately 4×1011 molecules cm−3 s. The constant extent of oxidation suggests that atmospheric aging results in a highly oxidized OA at these OH exposures, regardless of the aerosol source.

  19. Inhibition of synthesis of heparan sulfate by selenate: Possible dependence on sulfation for chain polymerization

    International Nuclear Information System (INIS)

    Dietrich, C.P.; Nader, H.B.; Buonassisi, V.; Colburn, P.

    1988-01-01

    Selenate, a sulfation inhibitor, blocks the synthesis of heparan sulfate and chondroitin sulfate by cultured endothelial cells. In contrast, selenate does not affect the production of hyaluronic acid, a nonsulfated glycosaminoglycan. No differences in molecular weight, [ 3 H]glucosamine/[ 35 S]sulfuric acid ratios, or disaccharide composition were observed when the heparan sulfate synthesized by selenate-treated cells was compared with that of control cells. The absence of undersulfated chains in preparations from cultures exposed to selenate supports the concept that, in the intact cell, the polymerization of heparan sulfate might be dependent on the sulfation of the saccharide units added to the growing glycosaminoglycan chain

  20. Periodate Oxidation for Sulfated Glycosaminoglycans, with Special Reference to the Position of Extra Sulfate Groups in Chondroitin Polysulfates, Chondroitin Sulfate D and Chondroitin Sulfate K

    OpenAIRE

    Seno, Nobuko; Murakami, Keiko; Shibusawa, Haru

    1981-01-01

    The optimum conditions for periodate oxidation of sulfated disaccharides were investigated to determine the position of extra sulfate groups on the saturated disulfated disaccharides obtained from chondroitin polysulfates, chondroitin sulfates D and K. Under the conditions: 2mM saturated disulfated disaccharide with 20mM sodium periodate at 37°in the dark, the uronic acid residue in the disulfated disaccharide from chondroitin sulfate D was rapidly and completely destroyed, whereas that in th...

  1. Characterization of urban aerosol using aerosol mass spectrometry and proton nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cleveland, M. J.; Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Lefer, B.; Rappenglück, B.

    2012-07-01

    Particulate matter was measured during August and September of 2006 in Houston as part of the Texas Air Quality Study II Radical and Aerosol Measurement Project. Aerosol size and composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Aerosol was dominated by sulfate (4.1 ± 2.6 μg m-3) and organic material (5.5 ± 4.0 μg m-3), with contributions of organic material from both primary (˜32%) and secondary (˜68%) sources. Secondary organic aerosol appears to be formed locally. In addition, 29 aerosol filter samples were analyzed using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine relative concentrations of organic functional groups. Houston aerosols are less oxidized than those observed elsewhere, with smaller relative contributions of carbon-oxygen double bonds. These particles do not fit 1H NMR source apportionment fingerprints for identification of secondary, marine, and biomass burning organic aerosol, suggesting that a new fingerprint for highly urbanized and industrially influenced locations be established.

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

    International Nuclear Information System (INIS)

    Buzatu, Andrei; Dill, Harald G.; Buzgar, Nicolae; Damian, Gheorghe; Maftei, Andreea Elena; Apopei, Andrei Ionuț

    2016-01-01

    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

  3. 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

  4. 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 0,2X3 and Y3 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.

  5. Sensitivity studies of different aerosol indirect effects in mixed-phase clouds

    Directory of Open Access Journals (Sweden)

    C. Hoose

    2009-11-01

    Full Text Available Aerosols affect the climate system by changing cloud characteristics. Using the global climate model ECHAM5-HAM, we investigate different aerosol effects on mixed-phase clouds: The glaciation effect, which refers to a more frequent glaciation due to anthropogenic aerosols, versus the de-activation effect, which suggests that ice nuclei become less effective because of an anthropogenic sulfate coating. The glaciation effect can partly offset the indirect aerosol effect on warm clouds and thus causes the total anthropogenic aerosol effect to be smaller. It is investigated by varying the parameterization for the Bergeron-Findeisen process and the threshold coating thickness of sulfate (SO4-crit, which is required to convert an externally mixed aerosol particle into an internally mixed particle. Differences in the net radiation at the top-of-the-atmosphere due to anthropogenic aerosols between the different sensitivity studies amount up to 0.5 W m−2. This suggests that the investigated mixed-phase processes have a major effect on the total anthropogenic aerosol effect.

  6. Enhanced sulfate reduction with acidogenic sulfate-reducing bacteria

    International Nuclear Information System (INIS)

    Wang Aijie; Ren Nanqi; Wang Xu; Lee Duujong

    2008-01-01

    Sulfate reduction in a continuous flow, acidogenic reactor using molasses wastewater as the carbon source was studied at varying chemical oxygen demand/sulfate (COD/SO 4 2- ) ratios. At a critical COD/SO 4 2- ratio of 2.7, neither COD nor sulfate were in excess for extra production of ethanol or acetate in the reactor. An acetic-type microbial metabolism was established with sulfate-reducing bacteria (SRB) significantly consuming hydrogen and volatile fatty acids produced by acidogenic bacteria and hydrogen producing acetogens in degrading COD, thereby yielding sulfate removal rate >94.6%. A low critical COD/SO 4 2- ratio of 1.6 was also observed with the enriched ASRB population in reactor which overcomes the barrier to the treatment capability of sulfate-laden wastewater treatment with limited COD supply

  7. The synthesis of taurine-conjugated bile acids and bile acid sulfates labeled with 14C or 3H in the taurine moiety

    International Nuclear Information System (INIS)

    Jie Zhang; Griffiths, W.J.; Sjoevall, Jan

    1997-01-01

    Studies of bile acid transport systems require radio-labeled taurine-conjugated bile acids with high specific activity. An established procedure was optimized to provide mild, fast, and effective conjugation of radio-labeled taurine with different types of bile acids, including those with labile 7α-hydroxy-3-oxo-Δ 4 or 3β, 7α-dihydroxy-Δ 5 structures. Taurine labeled with 14 C or 3 H was reacted with excess bile acid anhydride formed from the tributylamine salt and ethylchloroformate (2/1 M/M) in aqueous dioxane for 15 min at room temperature. The yields were higher than 95% and less than 2% side products were formed. Bile acid sulfates were conjugated with 14 C- or 3 H-labeled taurine by using N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline as the coupling reagent. The products were effectively purified by chromatography of the sodium salts on Sephadex LH-20. The yields of taurine-conjugated bile acid sulfates were 65-70%. (author)

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

    DEFF Research Database (Denmark)

    Beucher, Amélie; Boman, A; Mattbäck, S

    impact through the resulting corrosion of concrete and steel infrastructures, or their poor geotechnical qualities.Mapping acid sulfate soil occurrence thus constitutes a key step to target the strategic areas for subsequent environmental risk management and mitigation. Conventional mapping (i.e. soil...

  9. Decade of stratospheric sulfate measurements compared with observations of volcanic eruptions

    International Nuclear Information System (INIS)

    Sedlacek, W.A.; Mroz, E.J.; Lazrus, A.L.; Gandrud, B.W.

    1983-01-01

    Sulfate aerosol concentrations in the stratosphere have been measured for 11 years (1971--1981) using portions of filters collected by the Department of Energy's High Altitude Sampling Program. Data collected seasonally at altitudes between 13 km and 20 km spanning latitudes from 75 0 N to 51 0 S are reported. These data are compared with the reported altitudes of volcanic eruption plumes during the same decade. From this comparison it is concluded that (1) several unreported volcanic eruptions or eruptions to altitudes higher than reported did occur during the decade, (2) the e-fold removal time for sulfate aerosol from the stratosphere following the eruption of Volcan Fuego in 1974 was 11.2 +- 1.2 months, (3) the volcanic contribution to the average stratospheric sulfate concentration over the decade was greater than 50%, and (4) there may be evidence for an anthropogenic contribution to stratospheric sulfate that increases at the rate of 6 to 8% per year

  10. A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

    Science.gov (United States)

    Sareen, N.; McNeill, V. F.

    2011-12-01

    In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used

  11. The roles of sulfuric acid in new particle formation and growth in the mega-city of Beijing

    Directory of Open Access Journals (Sweden)

    D. L. Yue

    2010-05-01

    Full Text Available Simultaneous measurements of gaseous sulfuric acid and particle number size distributions were performed to investigate aerosol nucleation and growth during CAREBeijing-2008. The analysis of the measured aerosols and sulfuric acid with an aerosol dynamic model shows the dominant role of sulfuric acid in new particle formation (NPF process but also in the subsequent growth in Beijing. Based on the data of twelve NPF events, the average formation rates (2–13 cm−3 s−1 show a linear correlation with the sulfuric acid concentrations (R2=0.85. Coagulation seems to play a significant role in reducing the number concentration of nucleation mode particles with the ratio of the coagulation loss to formation rate being 0.41±0.16. The apparent growth rates vary from 3 to 11 nm h−1. Condensation of sulfuric acid and its subsequent neutralization by ammonia and coagulation contribute to the apparent particle growth on average 45±18% and 34±17%, respectively. The 30% higher concentration of sulfate than organic compounds in particles during the seven sulfur-rich NPF events but 20% lower concentration of sulfate during the five sulfur-poor type suggest that organic compounds are an important contributor to the growth of the freshly nucleated particles, especially during the sulfur-poor cases.

  12. Primary aerosol and secondary inorganic aerosol budget over the Mediterranean Basin during 2012 and 2013

    Science.gov (United States)

    Guth, Jonathan; Marécal, Virginie; Josse, Béatrice; Arteta, Joaquim; Hamer, Paul

    2018-04-01

    In the frame of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), we analyse the budget of primary aerosols and secondary inorganic aerosols over the Mediterranean Basin during the years 2012 and 2013. To do this, we use two year-long numerical simulations with the chemistry-transport model MOCAGE validated against satellite- and ground-based measurements. The budget is presented on an annual and a monthly basis on a domain covering 29 to 47° N latitude and 10° W to 38° E longitude. The years 2012 and 2013 show similar seasonal variations. The desert dust is the main contributor to the annual aerosol burden in the Mediterranean region with a peak in spring, and sea salt being the second most important contributor. The secondary inorganic aerosols, taken as a whole, contribute a similar level to sea salt. The results show that all of the considered aerosol types, except for sea salt aerosols, experience net export out of our Mediterranean Basin model domain, and thus this area should be considered as a source region for aerosols globally. Our study showed that 11 % of the desert dust, 22.8 to 39.5 % of the carbonaceous aerosols, 35 % of the sulfate and 9 % of the ammonium emitted or produced into the study domain are exported. The main sources of variability for aerosols between 2012 and 2013 are weather-related variations, acting on emissions processes, and the episodic import of aerosols from North American fires. In order to assess the importance of the anthropogenic emissions of the marine and the coastal areas which are central for the economy of the Mediterranean Basin, we made a sensitivity test simulation. This simulation is similar to the reference simulation but with the removal of the international shipping emissions and the anthropogenic emissions over a 50 km wide band inland along the coast. We showed that around 30 % of the emissions of carbonaceous aerosols and 35 to 60 % of the exported carbonaceous aerosols originates from the marine and

  13. Contemporaneous deposition of phyllosilicates and sulfates: Using Australian acidic saline lake deposits to describe geochemical variability on Mars

    Science.gov (United States)

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

    2009-01-01

    Studies of the origin of the Martian sulfate and phyllosilicate deposits have led to the hypothesis that there was a marked, global-scale change in the Mars environment from circum-neutral pH aqueous alteration in the Noachian to an acidic evaporitic system in the late Noachian to Hesperian. However, terrestrial studies suggest that two different geochemical systems need not be invoked to explain such geochemical variation.Western Australian acidic playa lakes have large pH differences separated vertically and laterally by only a few tens of meters, demonstrating how highly variable chemistries can coexist over short distances in natural environments. We suggest diverse and variable Martian aqueous environments where the coetaneous formation of phyllosilicates and sulfates at the Australian sites are analogs for regions where phyllosilicates and sulfates coexist on Mars. In these systems, Fe and alkali earth phyllosilicates represent deep facies associated with upwelling neutral to alkaline groundwater, whereas aluminous phyllosilicates and sulfates represent near-surface evaporitic facies formed from more acidic brines. Copyright 2009 by the American Geophysical Union.

  14. Is Distant Pollution Contaminating Local Air? Analyzing the Origins of Atmospheric Aerosols

    Directory of Open Access Journals (Sweden)

    David Geng

    2012-01-01

    Full Text Available Understanding the origin of aerosols in the atmosphere is important because of visual pollution, climate impacts, and deleterious health effects due to the inhalation of fine particles. This research analyzed aerosols characterized by their chloride, sulfate, and nitrate content as a function of size over a 3-month period. Due to wind patterns over coal-burning power plants, a higher concentration of local sulfate pollution was expected. Aerosols were harvested on the Purdue University campus using a high-volume air sampler with glass fiber filters and a five-stage impactor that separates the aerosols into five sizes. The filters were extracted in water to dissolve anions and the solution was analyzed using high-pressure liquid ion chromatography. Only trace amounts of chloride with no distinct patterns in size were detected. In total, nitrate content ranged from 0.12 to 2.10 μg/m3 and sulfate content ranged from 0.44 to 6.45 μg/m3 over a 3-month period. As for fine particles, a higher concentration of sulfate was observed. The Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT model determines air mass origin, and in this study, higher total sulfate content was observed when the air mass moved out of the southwest, and higher total nitrate content was observed when the air mass originated from the southeast. The author concluded that small particles resulted in sulfate from sulfur dioxide, typically from gas to particle conversion. High sulfur dioxide levels are directly correlated with coal-burning power plant density. Small particulate sulfate found in West Lafayette, Indiana, was determined to originate primarily from power plants in southwest Indiana. Though the results do show a significant amount of potentially harmful aerosols in West Lafayette, there is still further research to be done concerning isotopic composition of those particles in attempts to better explain the chemical pathways.

  15. MATRIX (Multiconfiguration Aerosol TRacker of mIXing state: an aerosol microphysical module for global atmospheric models

    Directory of Open Access Journals (Sweden)

    S. E. Bauer

    2008-10-01

    Full Text Available A new aerosol microphysical module MATRIX, the Multiconfiguration Aerosol TRacker of mIXing state, and its application in the Goddard Institute for Space Studies (GISS climate model (ModelE are described. This module, which is based on the quadrature method of moments (QMOM, represents nucleation, condensation, coagulation, internal and external mixing, and cloud-drop activation and provides aerosol particle mass and number concentration and particle size information for up to 16 mixed-mode aerosol populations. Internal and external mixing among aerosol components sulfate, nitrate, ammonium, carbonaceous aerosols, dust and sea-salt particles are represented. The solubility of each aerosol population, which is explicitly calculated based on its soluble and insoluble components, enables calculation of the dependence of cloud drop activation on the microphysical characterization of multiple soluble aerosol populations.

    A detailed model description and results of box-model simulations of various aerosol population configurations are presented. The box model experiments demonstrate the dependence of cloud activating aerosol number concentration on the aerosol population configuration; comparisons to sectional models are quite favorable. MATRIX is incorporated into the GISS climate model and simulations are carried out primarily to assess its performance/efficiency for global-scale atmospheric model application. Simulation results were compared with aircraft and station measurements of aerosol mass and number concentration and particle size to assess the ability of the new method to yield data suitable for such comparison. The model accurately captures the observed size distributions in the Aitken and accumulation modes up to particle diameter 1 μm, in which sulfate, nitrate, black and organic carbon are predominantly located; however the model underestimates coarse-mode number concentration and size, especially in the marine environment

  16. Performance and microbial community dynamics of a sulfate-reducing bioreactor treating coal generated acid mine drainage.

    Science.gov (United States)

    Burns, Andrew S; Pugh, Charles W; Segid, Yosief T; Behum, Paul T; Lefticariu, Liliana; Bender, Kelly S

    2012-06-01

    The effectiveness of a passive flow sulfate-reducing bioreactor processing acid mine drainage (AMD) generated from an abandoned coal mine in Southern Illinois was evaluated using geochemical and microbial community analysis 10 months post bioreactor construction. The results indicated that the treatment system was successful in both raising the pH of the AMD from 3.09 to 6.56 and in lowering the total iron level by 95.9%. While sulfate levels did decrease by 67.4%, the level post treatment (1153 mg/l) remained above recommended drinking water levels. Stimulation of biological sulfate reduction was indicated by a +2.60‰ increase in δ(34)S content of the remaining sulfate in the water post-treatment. Bacterial community analysis targeting 16S rRNA and dsrAB genes indicated that the pre-treated samples were dominated by bacteria related to iron-oxidizing Betaproteobacteria, while the post-treated water directly from the reactor outflow was dominated by sequences related to sulfur-oxidizing Epsilonproteobacteria and complex carbon degrading Bacteroidetes and Firmicutes phylums. Analysis of the post-treated water, prior to environmental release, revealed that the community shifted back to predominantly iron-oxidizing Betaproteobacteria. DsrA analysis implied limited diversity in the sulfate-reducing population present in both the bioreactor outflow and oxidation pond samples. These results support the use of passive flow bioreactors to lower the acidity, metal, and sulfate levels present in the AMD at the Tab-Simco mine, but suggest modifications of the system are necessary to both stimulate sulfate-reducing bacteria and inhibit sulfur-oxidizing bacteria.

  17. Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance

    Directory of Open Access Journals (Sweden)

    I. R. Zamora

    2013-09-01

    Full Text Available The hygroscopic growth of atmospheric particles affects atmospheric chemistry and Earth's climate. Water-soluble organic carbon (WSOC constitutes a significant fraction of the dry submicron mass of atmospheric aerosols, thus affecting their water uptake properties. Although the WSOC fraction is comprised of many compounds, a set of model substances can be used to describe its behavior. For this study, mixtures of Nordic aquatic fulvic acid reference (NAFA and Fluka humic acid (HA, with various combinations of inorganic salts (sodium chloride and ammonium sulfate and other representative organic compounds (levoglucosan and succinic acid, were studied. We measured the equilibrium water vapor pressure over bulk solutions of these mixtures as a function of temperature and solute concentration. New water activity (aw parameterizations and hygroscopic growth curves at 25 °C were calculated from these data for particles of equivalent composition. We examined the effect of temperature on the water activity and found a maximum variation of 9% in the 0–30 °C range, and 2% in the 20–30 °C range. Five two-component mixtures were studied to understand the effect of adding a humic substance (HS, such as NAFA and HA, to an inorganic salt or a saccharide. The deliquescence point at 25 °C for HS-inorganic mixtures did not change significantly from that of the pure inorganic species. However, the hygroscopic growth of HA / inorganic mixtures was lower than that exhibited by the pure salt, in proportion to the added mass of HA. The addition of NAFA to a highly soluble solute (ammonium sulfate, sodium chloride or levoglucosan in water had the same effect as the addition of HA to the inorganic species for most of the water activity range studied. Yet, the water uptake of these NAFA mixtures transitioned to match the growth of the pure salt or saccharide at high aw values. The remaining four mixtures were based on chemical composition data for different

  18. Hygroscopic properties of organic and inorganic aerosols[Dissertation 17260

    Energy Technology Data Exchange (ETDEWEB)

    Sjoegren, N O Staffan

    2007-07-01

    The atmosphere contains gases and particulate matter (aerosol). Organic material is present both in the gas phase and in the aerosol phase. Biogenic sources such as vegetation and anthropogenic sources such as biomass burning, fossil fuel use and various industries contribute to their emissions. The study of organic compounds in aerosol particles is of importance because they affect the water uptake (hygroscopicity) of inorganic aerosol, and hence the radiation budget of the Earth through the direct and indirect aerosol effects. The hygroscopicity of mixed organic/inorganic aerosol particles produced in the laboratory was characterized. This work reports on the following substances, and mixtures of them with ammonium sulfate (AS): adipic acid (AA), citric acid (CA), glutaric acid (GA) and humic acid sodium salt (NaHA). The AA and NaHA mixtures with AS were found to require up to tens of seconds for equilibrium water content to be reached. Therefore, measurements carried out on timescales shorter than a few seconds underestimate the hygroscopic growth factor (GF) with up to 10%, for samples containing a solid phase. Conversely, the GA and CA mixtures with AS were found to take up water readily and were well described by the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. The distinct deliquescence and efflorescence points of AS could be seen to gradually disappear as the CA content was increased. Furthermore mineral dust (standard Arizona test dust) was investigated, as well as the influence of nitric acid (HNO{sub 3}) uptake thereon. Mineral dust is hydrophobic, but after processing with HNO{sub 3} turns slightly hygroscopic. Large amounts of dust are injected to the atmosphere (largely from the Sahara and the Gobi deserts, but also from human land-use). Mineral dust is important as ice nuclei, and due to its larger sizes it can also contribute as cloud condensation nuclei. Mineral dust also offers surface for heterogeneous chemistry, and can play an important role

  19. Modelling of Aerosol Chemistry and Transport over Europe and Comparison with Measurements

    NARCIS (Netherlands)

    Jeuken, A.; Veefkind, J.P.; Metzger, S.; Denter, F.; Velthoven, P.

    1999-01-01

    Because of the short lifetime of aerosols (days-weeks), the radiative forcing associated with aerosols varies strongly spatially and temporally (see van Dorland et al., poster) Current measurement networks of sulfate and other aerosol species are unable to provide a representative picture of the

  20. Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

    Science.gov (United States)

    Liu, Tengyu; Huang, Dan Dan; Li, Zijun; Liu, Qianyun; Chan, ManNin; Chan, Chak K.

    2018-04-01

    The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm-3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm-3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m / z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors

  1. Evolution of Asian aerosols during transpacific transport in INTEX-B

    Energy Technology Data Exchange (ETDEWEB)

    Dunlea, E. J.; DeCarlo, Peter; Aiken, Allison; Kimmel, Joel; Peltier, R. E.; Weber, R. J.; Tomlinson, Jason M.; Collins, Donald R.; Shinozuka, Yohei; McNaughton, C. S.; Howell, S. G.; Clarke, A. D.; Emmons, L.; Apel, Eric; Pfister, G. G.; van Donkelaar, A.; Martin, R. V.; Millet, D. B.; Heald, C. L.; Jimenez, J. L.

    2009-10-01

    Measurements of aerosol composition were made with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) on board the NSF/NCAR C-130 aircraft as part of the Intercontinental Chemical Transport Experiment Phase B 5 (INTEX-B) field campaign over the Eastern Pacific Ocean. The HR-ToF-AMS measurements of non-refractory submicron aerosol mass are shown to compare well with other aerosol instrumentation in the INTEX-B field study. Two case studies are described for pollution layers transported across the Pacific from the Asian continent, intercepted 3–4 days and 7–10 days downwind of Asia, respectively. Aerosol chemistry is shown to 10 be a robust tracer for air masses originating in Asia, specifically the presence of sulfate dominated aerosol is a distinguishing feature of Asian pollution layers that have been transported to the Eastern Pacific. We examine the time scales of processing for sulfate and organic aerosol in the atmosphere and show that our observations confirm a conceptual model for transpacific transport from Asia proposed by Brock et al. (2004). 15 Our observations of both sulfate and organic aerosol in aged Asian pollution layers are consistent with fast formation near the Asian continent, followed by washout during lofting and subsequent transformation during transport across the Pacific. Our observations are the first atmospheric measurements to indicate that although secondary organic aerosol (SOA) formation from pollution happens on the timescale of one day, 20 the oxidation of organic aerosol continues at longer timescales in the atmosphere. Comparisons with chemical transport models of data from the entire campaign reveal an under-prediction of SOA mass in the MOZART model, but much smaller discrepancies with the GEOS-Chem model than found in previous studies over the Western Pacific. No evidence is found to support a previous hypothesis for significant secondary 25 organic aerosol formation in the free troposphere.

  2. Differentiating chondroitin sulfate glycosaminoglycans using collision-induced dissociation; uronic acid cross-ring diagnostic fragments in a single stage of tandem mass spectrometry.

    Science.gov (United States)

    Kailemia, Muchena J; Patel, Anish B; Johnson, Dane T; Li, Lingyun; Linhardt, Robert J; Amster, I Jonathan

    2015-01-01

    The stereochemistry of the hexuronic acid residues of the structure of glycosaminoglycans (GAGs) is a key feature that affects their interactions with proteins and other biological functions. Electron based tandem mass spectrometry methods, in particular electron detachment dissociation (EDD), have been able to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA) residues in some heparan sulfate tetrasaccharides by producing epimer-specific fragments. Similarly, the relative abundance of glycosidic fragment ions produced by collision-induced dissociation (CID) or EDD has been shown to correlate with the type of hexuronic acid present in chondroitin sulfate GAGs. The present work examines the effect of charge state and degree of sodium cationization on the CID fragmentation products that can be used to distinguish GlcA and IdoA containing chondroitin sulfate A and dermatan sulfate chains. The cross-ring fragments (2,4)A(n) and (0,2)X(n) formed within the hexuronic acid residues are highly preferential for chains containing GlcA, distinguishing it from IdoA. The diagnostic capability of the fragments requires the selection of a molecular ion and fragment ions with specific ionization characteristics, namely charge state and number of ionizable protons. The ions with the appropriate characteristics display diagnostic properties for all the chondroitin sulfate and dermatan sulfate chains (degree of polymerization of 4-10) studied.

  3. 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.

  4. The oxidation of SO2 by NO2(g) at the air-water interface of aquated aerosol: implications for the rapid onset of haze-aerosol events in China

    Science.gov (United States)

    Li, L.; Colussi, A. J.; Hoffmann, M. R.

    2017-12-01

    Aqueous phase chemistry plays a vital role in the global atmosphere. The importance of heterogeneous chemistry has been recently underscored by the severe haze-fog pollution episodes experienced in Chinese megacities. A key finding is that despite reduced photochemistry during the wintertime haze events, the oxidation of S(IV) into sulfate aerosol occurs rapidly in spite of the low levels of ozone and H2O2. Field observations suggest that NO2 could serve as a suitable oxidant of S(IV) during the events under neutral pH conditions. However, the haze aerosols are mostly acidic. Furthermore, the air-water interface is more acidic than bulk-phase aquated system according to our recent findings. This work investigates the chemistry taking place as NO2(g) collides with the surface of aqueous S(IV) microdroplets as a function of pH to closely simulate actual haze aerosol events under atmospheric conditions. The reaction between NO2(g) and HSO3- (aq) is studied in situ under ambient temperature and pressure via online electrospray ionization mass spectrometry. The aqueous aerosols containing HSO3- is generated using a microjet which is exposed to NO2(g) alternatively, while the composition of the 1 nm interfacial liquid layer of the aerosol is instantaneously measured. The ratio of HSO3- to HSO4- is observed to decrease with the concomitant appearance of a strong m/z 62 signal upon NO2(g) exposure. The appearance of m/z 62 indicates the formation of NO3- via the disproportionation of NO2 (2NO2(g) + H2O (l) ⇌ H++NO3-(aq) + HONO(aq)) and thus impacts the ion-ion interactions of NO3- on the ratio of HSO3- to HSO4- in the outermost interfacial layers. Parallel experiments with NO3-(aq) additions are conducted to quantify the impact of NO3- on the the ratio, in order to unravel the contribution of NO2 to the oxidation of S(IV). After accounting for the HNO3 effect, it is concluded: (1) most NO2(g) is converted into NO3- via anion-catalyzed hydrolytic disproportionation; (2

  5. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Science.gov (United States)

    Chung Kwong, Kai; Chim, Man Mei; Davies, James F.; Wilson, Kevin R.; Nin Chan, Man

    2018-02-01

    Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4-) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O) and a sulfate radical anion (SO4 ṡ -) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10-13 cm3 molecule-1 s-1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 1012 molecule cm-3 s), only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

  6. Formation of secondary inorganic aerosols by power plant emissions exhausted through cooling towers in Saxony.

    Science.gov (United States)

    Hinneburg, Detlef; Renner, Eberhard; Wolke, Ralf

    2009-01-01

    The fraction of ambient PM10 that is due to the formation of secondary inorganic particulate sulfate and nitrate from the emissions of two large, brown-coal-fired power stations in Saxony (East Germany) is examined. The power stations are equipped with natural-draft cooling towers. The flue gases are directly piped into the cooling towers, thereby receiving an additionally intensified uplift. The exhausted gas-steam mixture contains the gases CO, CO2, NO, NO2, and SO2, the directly emitted primary particles, and additionally, an excess of 'free' sulfate ions in water solution, which, after the desulfurization steps, remain non-neutralized by cations. The precursor gases NO2 and SO2 are capable of forming nitric and sulfuric acid by several pathways. The acids can be neutralized by ammonia and generate secondary particulate matter by heterogeneous condensation on preexisting particles. The simulations are performed by a nested and multi-scale application of the online-coupled model system LM-MUSCAT. The Local Model (LM; recently renamed as COSMO) of the German Weather Service performs the meteorological processes, while the Multi-scale Atmospheric Transport Model (MUSCAT) includes the transport, the gas phase chemistry, as well as the aerosol chemistry (thermodynamic ammonium-sulfate-nitrate-water system). The highest horizontal resolution in the inner region of Saxony is 0.7 km. One summer and one winter episode, each realizing 5 weeks of the year 2002, are simulated twice, with the cooling tower emissions switched on and off, respectively. This procedure serves to identify the direct and indirect influences of the single plumes on the formation and distribution of the secondary inorganic aerosols. Surface traces of the individual tower plumes can be located and distinguished, especially in the well-mixed boundary layer in daytime. At night, the plumes are decoupled from the surface. In no case does the resulting contribution of the cooling tower emissions to PM10

  7. Is there an aerosol signature of aqueous processing?

    Science.gov (United States)

    Ervens, B.; Sorooshian, A.

    2017-12-01

    The formation of aerosol mass in cloud water has been recognized as a substantial source of atmospheric aerosol mass. While sulfate formation can be relatively well constrained, the formation of secondary organic aerosol mass in the aqueous phase (aqSOA) is much more complex due to the multitude of precursors and variety in chemical processes. Aqueous phase processing adds aerosol mass to the droplet mode, which is formed due to mass addition to activated particles in clouds. In addition, it has been shown that aqSOA mass has specific characteristics in terms of oxidation state and hygroscopicity that might help to distinguish it from other SOA sources. Many models do not include detailed chemical mechanisms of sulfate and aqSOA formation and also lack details on the mass distribution of newly formed mass. Mass addition inside and outside clouds modifies different parts of an aerosol population and consequently affects predictions of properties and lifetime of particles. Using a combination of field data analysis and model studies for a variety of air masses, we will show which chemical and physical aerosol properties can be used, in order to identify an `aqueous phase signature' in processed aerosol populations. We will discuss differences in this signature in clean (e.g., background), moderately polluted (e.g., urban) and highly polluted (e.g., biomass burning) air masses and suggest air-mass-specific chemical and/or physical properties that will help to quantify the aqueous-phase derived aerosol mass.

  8. Effects of sulfate deprivation on the production of chondroitin/dermatan sulfate by cultures of skin fibroblasts from normal and diabetic individuals

    International Nuclear Information System (INIS)

    Silbert, C.K.; Humphries, D.E.; Palmer, M.E.; Silbert, J.E.

    1991-01-01

    Human skin fibroblast monolayer cultures from two normal men, three Type I diabetic men, and one Type I diabetic woman were incubated with [3H]glucosamine in the presence of diminished concentrations of sulfate. Although total synthesis of [3H]chondroitin/dermatan glycosaminoglycans varied somewhat between cell lines, glycosaminoglycan production was not affected within any line when sulfate levels were decreased from 0.3 mM to 0.06 mM to 0.01 mM to 0 added sulfate. Lowering of sulfate concentrations resulted in diminished sulfation of chondroitin/dermatan in a progressive manner, so that overall sulfation dropped to as low as 19% for one of the lines. Sulfation of chondroitin to form chondroitin 4-sulfate and chondroitin 6-sulfate was progressively and equally affected by decreasing the sulfate concentration in the culture medium. However, sulfation to form dermatan sulfate was preserved to a greater degree, so that the relative proportion of dermatan sulfate to chondroitin sulfate increased. Essentially all the nonsulfated residues were susceptible to chondroitin AC lyase, indicating that little epimerization of glucuronic acid residues to iduronic acid had occurred in the absence of sulfation. These results confirm the previously described dependency of glucuronic/iduronic epimerization on sulfation, and indicate that sulfation of the iduronic acid-containing disaccharide residues of dermatan can take place with sulfate concentrations lower than those needed for 6-sulfation and 4-sulfation of the glucuronic acid-containing disaccharide residues of chondroitin. There were considerable differences among the six fibroblast lines in susceptibility to low sulfate medium and in the proportion of chondroitin 6-sulfate, chondroitin 4-sulfate, and dermatan sulfate. However, there was no pattern of differences between normals and diabetics

  9. Multi-model comparison of the volcanic sulfate deposition from the 1815 eruption of Mt. Tambora

    Directory of Open Access Journals (Sweden)

    L. Marshall

    2018-02-01

    Full Text Available The eruption of Mt. Tambora in 1815 was the largest volcanic eruption of the past 500 years. The eruption had significant climatic impacts, leading to the 1816 year without a summer, and remains a valuable event from which to understand the climatic effects of large stratospheric volcanic sulfur dioxide injections. The eruption also resulted in one of the strongest and most easily identifiable volcanic sulfate signals in polar ice cores, which are widely used to reconstruct the timing and atmospheric sulfate loading of past eruptions. As part of the Model Intercomparison Project on the climatic response to Volcanic forcing (VolMIP, five state-of-the-art global aerosol models simulated this eruption. We analyse both simulated background (no Tambora and volcanic (with Tambora sulfate deposition to polar regions and compare to ice core records. The models simulate overall similar patterns of background sulfate deposition, although there are differences in regional details and magnitude. However, the volcanic sulfate deposition varies considerably between the models with differences in timing, spatial pattern and magnitude. Mean simulated deposited sulfate on Antarctica ranges from 19 to 264 kg km−2 and on Greenland from 31 to 194 kg km−2, as compared to the mean ice-core-derived estimates of roughly 50 kg km−2 for both Greenland and Antarctica. The ratio of the hemispheric atmospheric sulfate aerosol burden after the eruption to the average ice sheet deposited sulfate varies between models by up to a factor of 15. Sources of this inter-model variability include differences in both the formation and the transport of sulfate aerosol. Our results suggest that deriving relationships between sulfate deposited on ice sheets and atmospheric sulfate burdens from model simulations may be associated with greater uncertainties than previously thought.

  10. 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.

  11. Organics, Meteoritic Material, and other Elements in High Altitude Aerosols

    Science.gov (United States)

    Mahoney, M.; Murphy, D. M.; Thomson, D. S.

    1998-01-01

    Recent in situ measurements of the chemical composition of single aerosol particles at altitudes up to 19 km have revealed a number of surprising features about ambient particles. Upper tropospheric aerosols in the study region often contained more organic material than sulfate.

  12. Global source attribution of sulfate concentration and direct and indirect radiative forcing

    Science.gov (United States)

    Yang, Yang; Wang, Hailong; Smith, Steven J.; Easter, Richard; Ma, Po-Lun; Qian, Yun; Yu, Hongbin; Li, Can; Rasch, Philip J.

    2017-07-01

    The global source-receptor relationships of sulfate concentrations, and direct and indirect radiative forcing (DRF and IRF) from 16 regions/sectors for years 2010-2014 are examined in this study through utilizing a sulfur source-tagging capability implemented in the Community Earth System Model (CESM) with winds nudged to reanalysis data. Sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate concentrations are primarily attributed to non-local sources from long-range transport. Regional source efficiencies of sulfate concentrations are higher over regions with dry atmospheric conditions and less export, suggesting that lifetime of aerosols, together with regional export, is important in determining regional air quality. The simulated global total sulfate DRF is -0.42 W m-2, with -0.31 W m-2 contributed by anthropogenic sulfate and -0.11 W m-2 contributed by natural sulfate, relative to a state with no sulfur emissions. In the Southern Hemisphere tropics, dimethyl sulfide (DMS) contributes 17-84 % to the total DRF. East Asia has the largest contribution of 20-30 % over the Northern Hemisphere mid- and high latitudes. A 20 % perturbation of sulfate and its precursor emissions gives a sulfate incremental IRF of -0.44 W m-2. DMS has the largest contribution, explaining -0.23 W m-2 of the global sulfate incremental IRF. Incremental IRF over regions in the Southern Hemisphere with low background aerosols is more sensitive to emission perturbation than that over the polluted Northern Hemisphere.

  13. 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.

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

    International Nuclear Information System (INIS)

    Xu, Dongyan; Ma, Hong; Cheng, Fei

    2014-01-01

    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

  15. 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 40days, 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

  16. Pore water sampling in acid sulfate soils: a new peeper method.

    Science.gov (United States)

    Johnston, Scott G; Burton, Edward D; Keene, Annabelle F; Bush, Richard T; Sullivan, Leigh A; Isaacson, Lloyd

    2009-01-01

    This study describes the design, deployment, and application of a modified equilibration dialysis device (peeper) optimized for sampling pore waters in acid sulfate soils (ASS). The modified design overcomes the limitations of traditional-style peepers, when sampling firm ASS materials over relatively large depth intervals. The new peeper device uses removable, individual cells of 25 mL volume housed in a 1.5 m long rigid, high-density polyethylene rod. The rigid housing structure allows the device to be inserted directly into relatively firm soils without requiring a supporting frame. The use of removable cells eliminates the need for a large glove-box after peeper retrieval, thus simplifying physical handling. Removable cells are easily maintained in an inert atmosphere during sample processing and the 25-mL sample volume is sufficient for undertaking multiple analyses. A field evaluation of equilibration times indicates that 32 to 38 d of deployment was necessary. Overall, the modified method is simple and effective and well suited to acquisition and processing of redox-sensitive pore water profiles>1 m deep in acid sulfate soil or any other firm wetland soils.

  17. Sulfate cooling effects on climate through in-cloud oxidation of anthropogenic SO2

    International Nuclear Information System (INIS)

    Lelieveld, J.; Heintzenberg, J.

    1992-01-01

    Anthropogenic SO 2 emissions may exert a significant cooling effect on climate in the Northern Hemisphere through backscattering of solar radiation by sulfate particles. Earlier estimates of the sulfate climate forcing were based on a limited number of sulfate-scattering correlation measurements from which a high sulfate-scattering efficiency was derived. Model results suggest that cloud processing of air is the underlying mechanism. aqueous phase oxidation of SO 2 into sulfate and the subsequent release of the dry aerosol by cloud evaporation render sulfate a much more efficient scatterer than through gas-phase SO 2 oxidation

  18. Aerosol quantification with the Aerodyne Aerosol Mass Spectrometer: detection limits and ionizer background effects

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2009-02-01

    Full Text Available Systematic laboratory experiments were performed to investigate quantification of various species with two versions of the Aerodyne Aerosol Mass Spectrometer, a Quadrupole Aerosol Mass Spectrometer (Q-AMS and a compact Time-of-Flight Aerosol Mass Spectrometer (c-ToF-AMS. Here we present a new method to continuously determine the detection limits of the AMS analyzers during regular measurements, yielding detection limit (DL information under various measurement conditions. Minimum detection limits range from 0.03 μg m−3 (nitrate, sulfate, and chloride up to 0.5 μg m−3 (organics for the Q-AMS. Those of the c-ToF-AMS are found between 0.003 μg m−3 (nitrate, sulfate and 0.03 μg m−3 (ammonium, organics. The DL values found for the c-ToF-AMS were ~10 times lower than those of the Q-AMS, mainly due to differences in ion duty cycle. Effects causing an increase of the detection limits include long-term instrument contamination, measurement of high aerosol mass concentrations and short-term instrument history. The self-cleaning processes which reduce the instrument background after measurement of large aerosol concentrations as well as the influences of increased instrument background on mass concentration measurements are discussed. Finally, improvement of detection limits by extension of averaging time intervals, selected or reduced ion monitoring, and variation of particle-to-background measurement ratio are investigated.

  19. Effects of cloudy/clear air mixing and droplet pH on sulfate aerosol formation in a coupled chemistry/climate global model

    Energy Technology Data Exchange (ETDEWEB)

    Molenkamp, C.R.; Atherton, C.A. [Lawrence Livermore National Lab., CA (United States); Penner, J.E.; Walton, J.J. [Michigan Univ., Ann Arbor, MI (United States). Dept. of Atmospheric, Oceanic and Space Sciences

    1996-10-01

    In this paper we will briefly describe our coupled ECHAM/GRANTOUR model, provide a detailed description of our atmospheric chemistry parameterizations, and discuss a couple of numerical experiments in which we explore the influence of assumed pH and rate of mixing between cloudy and clear air on aqueous sulfate formation and concentration. We have used our tropospheric chemistry and transport model, GRANTOUR, to estimate the life cycle and global distributions of many trace species. Recently, we have coupled GRANTOUR with the ECHAM global climate model, which provides several enhanced capabilities in the representation of aerosol interactions.

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

    Directory of Open Access Journals (Sweden)

    B. Ervens

    2010-09-01

    Full Text Available This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a oligomers, (b nitrogen-containing products, (c photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud chemistry for the same conditions (liquid water content, particle size.

    The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt. During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7.

    Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend

  1. The synthesis of taurine-conjugated bile acids and bile acid sulfates labeled with {sup 14}C or {sup 3}H in the taurine moiety

    Energy Technology Data Exchange (ETDEWEB)

    Jie Zhang; Griffiths, W.J.; Sjoevall, Jan [Karolinska Inst., Medical Biochemistry and Biophysics Dept., Stockholm (Sweden)

    1997-02-01

    Studies of bile acid transport systems require radio-labeled taurine-conjugated bile acids with high specific activity. An established procedure was optimized to provide mild, fast, and effective conjugation of radio-labeled taurine with different types of bile acids, including those with labile 7{alpha}-hydroxy-3-oxo-{Delta}{sup 4} or 3{beta}, 7{alpha}-dihydroxy-{Delta}{sup 5} structures. Taurine labeled with {sup 14}C or {sup 3}H was reacted with excess bile acid anhydride formed from the tributylamine salt and ethylchloroformate (2/1 M/M) in aqueous dioxane for 15 min at room temperature. The yields were higher than 95% and less than 2% side products were formed. Bile acid sulfates were conjugated with {sup 14}C- or {sup 3}H-labeled taurine by using N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline as the coupling reagent. The products were effectively purified by chromatography of the sodium salts on Sephadex LH-20. The yields of taurine-conjugated bile acid sulfates were 65-70%. (author).

  2. Geochemical, Sulfur Isotopic Characteristics and Source Contributions of Size-Aggregated Aerosols Collected in Baring Head, New Zealand.

    Science.gov (United States)

    Li, J.; Michalski, G. M.; Davy, P.; Harvey, M.; Wilkins, B. P.; Katzman, T. L.

    2017-12-01

    Sulfate aerosols are critical to the climate, human health, and the hydrological cycle in the atmosphere, yet the sources of sulfate in aerosols are not completely understood. In this work, we evaluated the sources of sulfate in size-aggregated aerosols from the Southern Pacific Ocean and the land of New Zealand using geochemical and isotopic analyses. Aerosols were collected at Baring Head, New Zealand between 6/30/15 to 8/4/16 using two collectors, one only collects Southern Pacific Ocean derived aerosols (open-ocean collector), the other collects aerosols from both the ocean and the land (all-direction collector). Each collector is equipped with two filters to sample size-aggregated aerosols (fine aerosols: NSS-SO42-, 70%), while coarse aerosols are dominated by sea-salt sulfate. However, some NSS-SO42- was also observed in coarse aerosols collected in summer, suggesting the presence of accumulation mode NSS-SO42- aerosols, which is possibly due to high summer biogenic DMS flux. The sources of sulfur in NSS-SO42- could be further determined by their d34S values. DMS emission is likely the sole sulfur source in the open-ocean collector as it shows constant DMS-like d34S signatures (15-18‰) throughout the year. Meanwhile, the d34S of NSS-SO42- in the all-direction collector display a seasonal trend: summer time d34S values are higher and DMS-like (15-18‰), indicating DMS emission is the dominant sulfur source; winter time d34S values are lower ( 6-12‰), therefore the sulfur is likely sourced from both DMS emission and terrestrial S input with low d34S values, such as volcanic activities, fossil fuel and wood burning.

  3. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    Science.gov (United States)

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-05

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  4. Coastal Antarctic aerosol: the seasonal pattern of its chemical composition and radionuclide content

    International Nuclear Information System (INIS)

    Wagenbach, D.; Goerlach, U.; Moser, K.; Muennich, K.O.

    1988-01-01

    At the German Antarctic research station (70 degrees S, 8 degrees W), long-term observations of the chemical and radio-chemical composition of atmospheric particulate matter were started in spring 1983. Based on the analysis of high-volume aerosol filters sampled continuously for nearly 5 years, concentration records of the following aerosol components are presented here: (a) major ions (sea-salt, sulfate, nitrate); (b) cosmogenic 7 Be and terrigeneous 210 Pb; (c) trace elements (crustal Mn, heavy metal Pb). All species mentioned, with the exception of stable and radioactive Pb, show annual cycles. The maximum occurs in austral summer for 7 Be, sulfate, and crustal Mn. For sea-salt, however, the maximum is found in local autumn, and for nitrate in local spring. In local summer, the enhanced 7 Be to 210 Pb ratio is attributed to intenser large scale vertical mixing. The pattern of total sulfate seems to be controlled by the nss-sulfate production from marine organo-sulfur species during local summer, whereas in polar night, nss-sulfate shows very low or even negative concentration. Crustal aerosol (indicated by Mn) shows a mean summer contribution of 16 ng/SCM which exceeds the mean winter level by more than a factor of two. Based on a mean wash-out ratio of 0.27x10 6 observed for 210 Pb bearing aerosol particles, a Pb snow concentration of 3.0 pg/g is deduced from the mean air concentration of 11 pg/SCM. (authors)

  5. Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

    Science.gov (United States)

    Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

    Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

  6. Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

    Science.gov (United States)

    Peng, Chao; Jing, Bo; Guo, Yu-Cong; Zhang, Yun-Hong; Ge, Mao-Fa

    2016-02-25

    Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

  7. Breaks induced in the deoxyribonucleic acid of aerosolized Escherichia coli by ozonized cyclohexene.

    Science.gov (United States)

    De Mik, G; De Groot, I

    1978-01-01

    The inactivation of aerosolized Escherichia coli by ozone, cyclohexene, and ozonized cyclohexene was studied. The parameters for damage were loss of reproduction and introduction of breaks in the deoxyribonucleic acid (DNA). Aerosolization of E. coli in clean air at 80 percent relative humidity or in air containing either ozone or cyclohexene hardly affected survival; however, some breaks per DNA molecule were induced, as shown by sucrose gradient sedimentation of the DNA. Aerosolization of E. coli in air containing ozonized cyclohexene at 80 percent relative humidity decreased the survival by a factor of 10(3) or more after 1 h of exposure and induced many breaks in the DNA. PMID:341811

  8. 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.

  9. 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

  10. 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.

  11. 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.

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

    Science.gov (United States)

    Church, C.D.; Wilkin, R.T.; Alpers, Charles 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.

  13. Modeling the Sulfate Deposition to the Greenland Ice Sheet From the Laki Eruption

    Science.gov (United States)

    Oman, L.; Robock, A.; Stenchikov, G.; Thordarson, T.; Gao, C.

    2005-12-01

    Using the state of the art Goddard Institute for Space Studies (GISS) modelE general circulation model, simulations were conducted of the chemistry and transport of aerosols resulting from the 1783-84 Laki (64°N) flood lava eruption. A set of 3 ensemble simulations from different initial conditions were conducted by injecting our estimate of the SO2 gas into the atmosphere by the 10 episodes of the eruption and allowing the sulfur chemistry model to convert this gas into sulfate aerosol. The SO2 gas and sulfate aerosol is transported by the model and wet and dry deposition is calculated over each grid box during the simulation. We compare the resulting sulfate deposition to the Greenland Ice Sheet in the model to 23 ice core measurements and find very good agreement. The model simulation deposits a range of 169 to over 300 kg/km2 over interior Greenland with much higher values along the coastal areas. This compares to a range of 62 to 324 kg/km2 for the 23 ice core measurements with an average value of 158 kg/km2. This comparison is one important model validation tool. Modeling and observations show fairly large spatial variations in the deposition of sulfate across the Greenland Ice Sheet for the Laki eruption, but the patterns are similar to those we modeled for the 1912 Katmai and 1991 Pinatubo eruptions. Estimates of sulfate loading based on single ice cores can show significant differences, so ideally several ice cores should be combined in reconstructing the sulfate loading of past volcanic eruptions, taking into account the characteristic spatial variations in the deposition pattern.

  14. Improved detection of coastal acid sulfate soil hotspots through biomonitoring of metal(loid) accumulation in water lilies (Nymphaea capensis).

    Science.gov (United States)

    Stroud, Jacqueline L; Collins, Richard N

    2014-07-15

    Anthropogenically disturbed coastal acid sulfate soils along the east coast of Australia, and worldwide, periodically result in the discharge of acid waters containing high concentrations of metals. Identifying priority sites (hotspots) within a catchment for acid sulfate soil remediation activities typically involves long-term monitoring of drainwater chemistry, including the capture of data on unpredictable rain-induced groundwater discharge events. To improve upon this monitoring approach, this study investigated using the water lily (Nymphaea capensis) as a biomonitor of drainage waters to identify hotspots in three acid sulfate soil impacted catchments (83 km(2)) in north-eastern New South Wales, Australia. In one catchment where the location of hotspots was known, water lily lamina concentrations of a suite of metal(loid)s were significantly (photspots revealed within catchment variation of plant metal concentrations up to 70-fold. High resolution maps produced from these results, therefore, provided strong evidence for the location of potential hotspots which were confirmed with measurements of drainwater chemistry during rain-induced groundwater discharge events. Median catchment lily accumulation was ca. 160 mg Al kg(-1) and 1,300 mg Fe kg(-1), with hotspots containing up to 6- and 10-fold higher Al and Fe concentrations. These findings suggest that biomonitoring with N. capensis can be an important tool to rapidly identify priority sites for remediation in acid sulfate soil impacted landscapes. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Development of an Operational Multi-sensor and Multi-channel Aerosol Assimilation Package Using NAAPS and NAVDAS

    Science.gov (United States)

    2010-09-30

    5593-1, 2010, EGU General Assembly 2010. Shi, Y., J. Zhang, J. S. Reid, E. Hyer, Evaluation of MISR Aerosol Optical Depth Product for Aerosol Data...a surrogate for aerosol type, as large η values are generally related to fine mode aerosols, such as sulfate and smoke aerosols, and small η values

  16. Global direct radiative forcing by process-parameterized aerosol optical properties

    Science.gov (United States)

    KirkevâG, Alf; Iversen, Trond

    2002-10-01

    A parameterization of aerosol optical parameters is developed and implemented in an extended version of the community climate model version 3.2 (CCM3) of the U.S. National Center for Atmospheric Research. Direct radiative forcing (DRF) by monthly averaged calculated concentrations of non-sea-salt sulfate and black carbon (BC) is estimated. Inputs are production-specific BC and sulfate from [2002] and background aerosol size distribution and composition. The scheme interpolates between tabulated values to obtain the aerosol single scattering albedo, asymmetry factor, extinction coefficient, and specific extinction coefficient. The tables are constructed by full calculations of optical properties for an array of aerosol input values, for which size-distributed aerosol properties are estimated from theory for condensation and Brownian coagulation, assumed distribution of cloud-droplet residuals from aqueous phase oxidation, and prescribed properties of the background aerosols. Humidity swelling is estimated from the Köhler equation, and Mie calculations finally yield spectrally resolved aerosol optical parameters for 13 solar bands. The scheme is shown to give excellent agreement with nonparameterized DRF calculations for a wide range of situations. Using IPCC emission scenarios for the years 2000 and 2100, calculations with an atmospheric global cliamte model (AFCM) yield a global net anthropogenic DRF of -0.11 and 0.11 W m-2, respectively, when 90% of BC from biomass burning is assumed anthropogenic. In the 2000 scenario, the individual DRF due to sulfate and BC has separately been estimated to -0.29 and 0.19 W m-2, respectively. Our estimates of DRF by BC per BC mass burden are lower than earlier published estimates. Some sensitivity tests are included to investigate to what extent uncertain assumptions may influence these results.

  17. Bacteria and Acidic Drainage from Coal Refuse: Inhibition by Sodium Lauryl Sulfate and Sodium Benzoate

    OpenAIRE

    Dugan, Patrick R.; Apel, William A.

    1983-01-01

    The application of an aqueous solution of sodium lauryl sulfate and sodium benzoate to the surface of high-sulfur coal refuse resulted in the inhibition of iron-and sulfur-oxidizing chemoautotrophic bacteria and in the decrease of acidic drainage from the refuse, suggesting that acid drainage can be abated in the field by inhibiting iron- and sulfur-oxidizing bacteria.

  18. Global source attribution of sulfate concentration and direct and indirect radiative forcing

    Directory of Open Access Journals (Sweden)

    Y. Yang

    2017-07-01

    Full Text Available The global source–receptor relationships of sulfate concentrations, and direct and indirect radiative forcing (DRF and IRF from 16 regions/sectors for years 2010–2014 are examined in this study through utilizing a sulfur source-tagging capability implemented in the Community Earth System Model (CESM with winds nudged to reanalysis data. Sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate concentrations are primarily attributed to non-local sources from long-range transport. Regional source efficiencies of sulfate concentrations are higher over regions with dry atmospheric conditions and less export, suggesting that lifetime of aerosols, together with regional export, is important in determining regional air quality. The simulated global total sulfate DRF is −0.42 W m−2, with −0.31 W m−2 contributed by anthropogenic sulfate and −0.11 W m−2 contributed by natural sulfate, relative to a state with no sulfur emissions. In the Southern Hemisphere tropics, dimethyl sulfide (DMS contributes 17–84 % to the total DRF. East Asia has the largest contribution of 20–30 % over the Northern Hemisphere mid- and high latitudes. A 20 % perturbation of sulfate and its precursor emissions gives a sulfate incremental IRF of −0.44 W m−2. DMS has the largest contribution, explaining −0.23 W m−2 of the global sulfate incremental IRF. Incremental IRF over regions in the Southern Hemisphere with low background aerosols is more sensitive to emission perturbation than that over the polluted Northern Hemisphere.

  19. Aerosols at the poles: an AeroCom Phase II multi-model evaluation

    Directory of Open Access Journals (Sweden)

    M. Sand

    2017-10-01

    Full Text Available Atmospheric aerosols from anthropogenic and natural sources reach the polar regions through long-range transport and affect the local radiation balance. Such transport is, however, poorly constrained in present-day global climate models, and few multi-model evaluations of polar anthropogenic aerosol radiative forcing exist. Here we compare the aerosol optical depth (AOD at 550 nm from simulations with 16 global aerosol models from the AeroCom Phase II model intercomparison project with available observations at both poles. We show that the annual mean multi-model median is representative of the observations in Arctic, but that the intermodel spread is large. We also document the geographical distribution and seasonal cycle of the AOD for the individual aerosol species: black carbon (BC from fossil fuel and biomass burning, sulfate, organic aerosols (OAs, dust, and sea-salt. For a subset of models that represent nitrate and secondary organic aerosols (SOAs, we document the role of these aerosols at high latitudes.The seasonal dependence of natural and anthropogenic aerosols differs with natural aerosols peaking in winter (sea-salt and spring (dust, whereas AOD from anthropogenic aerosols peaks in late spring and summer. The models produce a median annual mean AOD of 0.07 in the Arctic (defined here as north of 60° N. The models also predict a noteworthy aerosol transport to the Antarctic (south of 70° S with a resulting AOD varying between 0.01 and 0.02. The models have estimated the shortwave anthropogenic radiative forcing contributions to the direct aerosol effect (DAE associated with BC and OA from fossil fuel and biofuel (FF, sulfate, SOAs, nitrate, and biomass burning from BC and OA emissions combined. The Arctic modelled annual mean DAE is slightly negative (−0.12 W m−2, dominated by a positive BC FF DAE in spring and a negative sulfate DAE in summer. The Antarctic DAE is governed by BC FF. We perform sensitivity

  20. Removal of sulfur dioxide and formation of sulfate aerosol in Tokyo

    Science.gov (United States)

    Miyakawa, T.; Takegawa, N.; Kondo, Y.

    2007-07-01

    Ground-based in situ measurements of sulfur dioxide (SO2) and submicron sulfate aerosol (SO42-) together with carbon monoxide (CO) were conducted at an urban site in Tokyo, Japan from spring 2003 to winter 2004. The observed concentrations of SO2 were affected dominantly by anthropogenic emissions (for example, manufacturing industries) in source areas, while small fraction of the data (sulfur compounds (SOx = SO2 + SO42-) and the remaining fraction of SOx, which is derived as the ratio of the linear regression slope of the SOx-CO correlation, is used as measures for the formation of SO42- and removal of SOx, respectively. Using these parameters, the average formation efficiency of SO42- (i.e., amount of SO42- produced per SO2 emitted from emission sources) are estimated to be 0.18 and 0.03 in the summer and winter periods, respectively. A simple box model was developed to estimate the lifetime of SOx. The lifetime of SOx for the summer period (26 h) is estimated to be about two times longer than that for the winter period (14 h). The seasonal variations of the remaining fraction of SOx, estimated formation efficiency of SO42-, and lifetime of SOx are likely due to those of the boundary layer height and photochemical activity (i.e., hydroxyl radical). These results provide useful insights into the formation and removal processes of sulfur compounds exported from an urban area.

  1. The impacts of aerosol loading, composition, and water uptake on aerosol extinction variability in the Baltimore–Washington, D.C. region

    Directory of Open Access Journals (Sweden)

    A. J. Beyersdorf

    2016-01-01

    Full Text Available In order to utilize satellite-based aerosol measurements for the determination of air quality, the relationship between aerosol optical properties (wavelength-dependent, column-integrated extinction measured by satellites and mass measurements of aerosol loading (PM2.5 used for air quality monitoring must be understood. This connection varies with many factors including those specific to the aerosol type – such as composition, size, and hygroscopicity – and to the surrounding atmosphere, such as temperature, relative humidity (RH, and altitude, all of which can vary spatially and temporally. During the DISCOVER-AQ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality project, extensive in situ atmospheric profiling in the Baltimore, MD–Washington, D.C. region was performed during 14 flights in July 2011. Identical flight plans and profile locations throughout the project provide meaningful statistics for determining the variability in and correlations between aerosol loading, composition, optical properties, and meteorological conditions. Measured water-soluble aerosol mass was composed primarily of ammonium sulfate (campaign average of 32 % and organics (57 %. A distinct difference in composition was observed, with high-loading days having a proportionally larger percentage of sulfate due to transport from the Ohio River Valley. This composition shift caused a change in the aerosol water-uptake potential (hygroscopicity such that higher relative contributions of inorganics increased the bulk aerosol hygroscopicity. These days also tended to have higher relative humidity, causing an increase in the water content of the aerosol. Conversely, low-aerosol-loading days had lower sulfate and higher black carbon contributions, causing lower single-scattering albedos (SSAs. The average black carbon concentrations were 240 ng m−3 in the lowest 1 km, decreasing to 35

  2. Rare earth sulfates

    International Nuclear Information System (INIS)

    Komissarova, L.N.; Shatskij, V.M.; Pokrovskij, A.N.; Chizhov, S.M.; Bal'kina, T.I.; Suponitskij, Yu.L.

    1986-01-01

    Results of experimental works on the study of synthesis conditions, structure and physico-chemical properties of rare earth, scandium and yttrium sulfates, have been generalized. Phase diagrams of solubility and fusibility, thermodynamic and crystallochemical characteristics, thermal stability of hydrates and anhydrous sulfates of rare earths, including normal, double (with cations of alkali and alkaline-earth metals), ternary and anion-mixed sulfates of rare earths, as well as their adducts, are considered. The state of ions of rare earths, scandium and yttrium in aqueous sulfuric acid solutions is discussed. Data on the use of rare earth sulfates are given

  3. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Directory of Open Access Journals (Sweden)

    K. C. Kwong

    2018-02-01

    Full Text Available Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4− has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O and a sulfate radical anion (SO4 ⋅ − upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19  ×  10−13 cm3 molecule−1 s−1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27  ×  1012 molecule cm−3 s, only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we

  4. The impact of aerosol composition on the particle to gas partitioning of reactive mercury.

    Science.gov (United States)

    Rutter, Andrew P; Schauer, James J

    2007-06-01

    A laboratory system was developed to study the gas-particle partitioning of reactive mercury (RM) as a function of aerosol composition in synthetic atmospheric particulate matter. The collection of RM was achieved by filter- and sorbent-based methods. Analyses of the RM collected on the filters and sorbents were performed using thermal extraction combined with cold vapor atomic fluorescence spectroscopy (CVAFS), allowing direct measurement of the RM load on the substrates. Laboratory measurements of the gas-particle partitioning coefficients of RM to atmospheric aerosol particles revealed a strong dependence on aerosol composition, with partitioning coefficients that varied by orders of magnitude depending on the composition of the particles. Particles of sodium nitrate and the chlorides of potassium and sodium had high partitioning coefficients, shifting the RM partitioning toward the particle phase, while ammonium sulfate, levoglucosan, and adipic acid caused the RM to partition toward the gas phase and, therefore, had partitioning coefficients that were lower by orders of magnitude.

  5. Aerosol composition and source apportionment in Santiago de Chile

    Science.gov (United States)

    Artaxo, Paulo; Oyola, Pedro; Martinez, Roberto

    1999-04-01

    Santiago de Chile, São Paulo and Mexico City are Latin American urban areas that suffer from heavy air pollution. In order to study air pollution in Santiago area, an aerosol source apportionment study was designed to measure ambient aerosol composition and size distribution for two downtown sampling sites in Santiago. The aerosol monitoring stations were operated in Gotuzo and Las Condes during July and August 1996. The study employed stacked filter units (SFU) for aerosol sampling, collecting fine mode aerosol (dpsource apportionment was performed using Absolute Principal Factor Analysis (APFA). Very high aerosol concentrations were observed (up to 400 μg/m 3 PM 10). The main aerosol particle sources in Santiago are resuspended soil dust and traffic emissions. Coarse particles account for 63% of PM 10 aerosol in Gotuzo and 53% in Las Condes. A major part of this component is resuspended soil dust. In the fine fraction, resuspended soil dust accounts for 15% of fine mass, and the aerosols associated with transportation activities account for a high 64% of the fine particle mass. Sulfate particle is an important component of the aerosol in Santiago, mainly originating from gas-to-particle conversion from SO 2. In the Gotuzo site, sulfates are the highest aerosol component, accounting for 64.5% of fine mass. Direct traffic emissions are generally mixed with resuspended soil dust. It is difficult to separate the two components, because the soil dust in downtown Santiago is contaminated with Pb, Br, Cl, and other heavy metals that are also tracers for traffic emissions. Residual oil combustion is observed, with the presence of V, S and Ni. An aerosol components from industrial emissions is also present, with the presence of several heavy metals such as Zn, Cu and others. A factor with molybdenum, arsenic, copper and sulfur was observed frequently, and it results from emissions of copper smelters.

  6. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    International Nuclear Information System (INIS)

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-01

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln 2 (phen) 2 (SO 4 ) 3 (H 2 O) 2 ] n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)] n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO 4 2− anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of 5 D 0 → 7 F J (J=0–4) of the Eu(III)

  7. Iduronic Acid in chondroitin/dermatan sulfate affects directional migration of aortic smooth muscle cells

    NARCIS (Netherlands)

    Bartolini, B.; Thelin, M.A.; Svensson, L.; Ghiselli, G.; Kuppevelt, T.H. van; Malmstrom, A.; Maccarana, M.

    2013-01-01

    Aortic smooth muscle cells produce chondroitin/dermatan sulfate (CS/DS) proteoglycans that regulate extracellular matrix organization and cell behavior in normal and pathological conditions. A unique feature of CS/DS proteoglycans is the presence of iduronic acid (IdoA), catalyzed by two DS

  8. SECONDARY ORGANIC AEROSOL FORMATION FROM THE OXIDATION OF AROMATIC HYDROCARBONS IN THE PRESENCE OF DRY SUBMICRON AMMONIUM SULFATE AEROSOL

    Science.gov (United States)

    A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas-aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds ...

  9. Future aerosols of the southwest - Implications for fundamental aerosol research

    International Nuclear Information System (INIS)

    Friedlander, S.K.

    1980-01-01

    It is shown that substantial increases in the use of coal in the U.S. will lead to substantial increases in emissions of particulate matter, SO/sub x/, and NO/sub x/ in the part of the U.S. west of the Mississippi. A shift in the primary particulate emissions from coarse to submicron particles is predicted. Attention is given to the nature of the submicron aerosol in the southwest, the distribution of sulfur with respect to particle size, the formation of new particles in the atmosphere, and the ammonium nitrate equilibrium. It is concluded that increased coal use will result in a 50% increase in SO/sub x/ emissions and a doubling of NO/sub x/ emissions in the western U.S. by the year 2000, that ambient levels of aerosol sulfates and nitrates will increase, and that a large increase in submicron aerosol mass is likely

  10. Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

    Directory of Open Access Journals (Sweden)

    K. Kawamura

    2012-11-01

    Full Text Available Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2 followed by malonic (C3 and/or succinic (C4 acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice was retreating. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (< 30 ng m−3, except for one sample (up to 70 ng m−3 that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coast of Antarctica. Because the marine aerosols that showed a depletion of C2 were collected under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III complex. We also determined stable carbon isotopic compositions (δ13C of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed −26.5‰ (range: −29.7 to −24.7‰, suggesting that marine aerosol carbon is derived

  11. Bacteria and Acidic Drainage from Coal Refuse: Inhibition by Sodium Lauryl Sulfate and Sodium Benzoate

    Science.gov (United States)

    Dugan, Patrick R.; Apel, William A.

    1983-01-01

    The application of an aqueous solution of sodium lauryl sulfate and sodium benzoate to the surface of high-sulfur coal refuse resulted in the inhibition of iron-and sulfur-oxidizing chemoautotrophic bacteria and in the decrease of acidic drainage from the refuse, suggesting that acid drainage can be abated in the field by inhibiting iron- and sulfur-oxidizing bacteria. PMID:16346347

  12. Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

    Directory of Open Access Journals (Sweden)

    T. Liu

    2018-04-01

    Full Text Available The formation of secondary organic aerosol (SOA has been widely studied in the presence of dry seed particles at low relative humidity (RH. At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm−3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm−3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m ∕ z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS, indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory

  13. 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

  14. Data assimilation of CALIPSO aerosol observations

    Directory of Open Access Journals (Sweden)

    T. T. Sekiyama

    2010-01-01

    Full Text Available We have developed an advanced data assimilation system for a global aerosol model with a four-dimensional ensemble Kalman filter in which the Level 1B data from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO were successfully assimilated for the first time, to the best of the authors' knowledge. A one-month data assimilation cycle experiment for dust, sulfate, and sea-salt aerosols was performed in May 2007. The results were validated via two independent observations: 1 the ground-based lidar network in East Asia, managed by the National Institute for Environmental Studies of Japan, and 2 weather reports of aeolian dust events in Japan. Detailed four-dimensional structures of aerosol outflows from source regions over oceans and continents for various particle types and sizes were well reproduced. The intensity of dust emission at each grid point was also corrected by this data assimilation system. These results are valuable for the comprehensive analysis of aerosol behavior as well as aerosol forecasting.

  15. Operational aerosol and dust storm forecasting

    International Nuclear Information System (INIS)

    Westphal, D L; Curtis, C A; Liu, M; Walker, A L

    2009-01-01

    The U. S. Navy now conducts operational forecasting of aerosols and dust storms on global and regional scales. The Navy Aerosol Analysis and Prediction System (NAAPS) is run four times per day and produces 6-day forecasts of sulfate, smoke, dust and sea salt aerosol concentrations and visibility for the entire globe. The Coupled Ocean Atmosphere Mesoscale Prediction System (COAMPS (registered) ) is run twice daily for Southwest Asia and produces 3-day forecasts of dust, smoke, and visibility. The graphical output from these models is available on the Internet (www.nrlmry.navy.mil/aerosol/). The aerosol optical properties are calculated for each specie for each forecast output time and used for sea surface temperature (SST) retrieval corrections, regional electro-optical (EO) propagation assessments, and the development of satellite algorithms. NAAPS daily aerosol optical depth (AOD) values are compared with the Advanced Very High Resolution Radiometer (AVHRR) and Moderate Resolution Imaging Spectroradiometer (MODIS) AOD values. Visibility forecasts are compared quantitatively with surface synoptic reports.

  16. Sensitivity of aerosol loading and properties to cloudiness

    Science.gov (United States)

    Iversen, T.; Seland, O.; Kirkevag, A.; Kristjansson, J. E.

    2005-12-01

    Clouds influence aerosols in various ways. Sulfate is swiftly produced in liquid phase provided there is both sulfur dioxide and oxidants available. Nucleation and Aitken mode aerosol particles efficiently grow in size by collision and coagulation with cloud droplets. When precipitation is formed, aerosol and precursor gases may be quickly removed bay rainout. The dynamics associated with clouds in some cases may swiftly mix aerosols deeply into the troposphere. In some cases Aitken-mode particles may be formed in cloud droplets by splitting agglomerates of particulate matter such as black carbon In this presentation we will discuss how global cloudiness may influence the burden, residence time, and spatial distribution of sulfate, black carbon and particulate organic matter. A similar physico-chemical scheme for there compounds has been implemented in three generations of the NCAR community climate model (CCM3, CAM2 and CAM3). The scheme is documented in the literature and is a part of the Aerocom-intercomparison. There are many differences between these models. With respect to aerosols, a major difference is that CAM3 has a considerably higher global cloud volume and more then twice the amount of cloud water than CAM2 and CCM3. Atmospheric simulations have been made with prescribed ocean temperatures. It is slightly surprising to discover that certain aspects of the aerosols are not particularly sensitive to these differences in cloud availability. This sensitivity will be compared to sensitivities with respect to processing in deep convective clouds.

  17. Effect of Salicylic Acid and Chelated Magnesium Sulfate on Fruit Quality Improvement (Physical Characteristics in Pear (cv. Louise Bonne

    Directory of Open Access Journals (Sweden)

    mahjabin adel

    2017-02-01

    Full Text Available Introduction: Fruit quality is described based on the crop functions (for industry or table and/or difference of the consumer tastes in different societies. The conformity of the quality with consumer demands has an effective role in improvement of the marketing process. For example, elongated pears are preferred for the processing industries and conserving productions. The lack of attention to retaining of quality and/or improvement of apparent situation of gardening product in proportion to consumer demands decreases especial consumer acceptance. The necessity of having desired quality characteristics in pear fruits from the characters viewpoint of fruit specific gravity (major rating criterion of pears and proportion of length to diameter (minor rating, because of their role in market acceptance and pricing, is evident. Fruit quality, while harvesting, as one of the components of plants fertility influenced under different parameters like nourishment and could be managed during growth season. In other words, the gain of qualities proportionated to consumers demands and/or processing industries is possible by the use of acquired method such as the kind of mother plant nutrition, and control of pests and diseases, etc. In the current research, the effect of salicylic acid and chelated magnesium sulfate was studied on physical indexes of fruits quality of pear fruit. Materials and Methods: In order to study the effect of treatment agents, an experiment was conducted in the ecological conditions of Qazvinon Pear trees belonging to Louise Bonne cultivar in the Randomized Complete Block Design. The treatments includecontrol group (with andwithout water,chelated magnesium sulfate with concentration of 0.5 gram in a liter, chelated magnesium sulfate with concentration of 0.7gram in a liter, salicylic acid with concentration of0.1 gram in a liter,the compound treatment of salicylic acid with concentration of 0.1 andchelated magnesium sulfate with

  18. Holothurian Fucosylated Chondroitin Sulfate

    Directory of Open Access Journals (Sweden)

    Vitor H. Pomin

    2014-01-01

    Full Text Available Fucosylated chondroitin sulfate (FucCS is a structurally distinct glycosaminoglycan found in sea cucumber species. It has the same backbone composition of alternating 4-linked glucuronic acid and 3-linked N-acetyl galactosamine residues within disaccharide repeating units as regularly found in mammalian chondroitin sulfates. However, FucCS has also sulfated fucosyl branching units 3-O-linked to the acid residues. The sulfation patterns of these branches vary accordingly with holothurian species and account for different biological actions and responses. FucCSs may exhibit anticoagulant, antithrombotic, anti-inflammatory, anticancer, antiviral, and pro-angiogenic activities, besides its beneficial effects in hemodialysis, cellular growth modulation, fibrosis and hyperglycemia. Through an historical overview, this document covers most of the science regarding the holothurian FucCS. Both structural and medical properties of this unique GAG, investigated during the last 25 years, are systematically discussed herein.

  19. Laboratory study of the effect of oxalic acid on the cloud condensation nuclei activity of mineral dust aerosol

    Science.gov (United States)

    Gierlus, Kelly M.; Laskina, Olga; Abernathy, Tricia L.; Grassian, Vicki H.

    2012-01-01

    Dicarboxylic acids, which make up a significant portion of the atmospheric organic aerosol, are emitted directly through biomass burning as well as produced through the oxidation of volatile organic compounds. Oxalic acid, the most abundant of the dicarboxylic acids, has been shown by recent field studies to be present in mineral dust aerosol particles. The presence of these internally mixed organic compounds can alter the water absorption and cloud condensation nuclei (CCN) abilities of mineral particles in the Earth's atmosphere. The University of Iowa's Multi-Analysis Aerosol Reactor System ( MAARS) was used to measure the CCN activity of internally mixed particles that were generated from a mixture of either calcite or polystyrene latex spheres (PSLs) in an aqueous solution of oxalic acid. Although PSL is not a mineral dust component, it is used here as a non-reactive, insoluble particle. CCN measurements indicate that the internally mixed oxalate/calcite particles showed nearly identical CCN activity compared to the original calcite particles whereas oxalic acid/PSL internally mixed particles showed much greater CCN activity compared to PSL particles alone. This difference is due to the reaction of calcite with oxalic acid, which produces a relatively insoluble calcium oxalate coating on the particle surface and not a soluble coating as it does on the PSL particle. Our results suggest that atmospheric processing of mineral dust aerosol through heterogeneous processes will likely depend on the mineralogy and the specific chemistry involved. Increase in the CCN activity by incorporation of oxalic acid are only expected for unreactive insoluble dust particles that form a soluble coating.

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

    Science.gov (United States)

    Nordstrom, D. Kirk; McCleskey, R. Blaine; 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.

  1. Heparan sulfate-chondroitin sulfate hybrid proteoglycan of the cell surface and basement membrane of mouse mammary epithelial cells

    International Nuclear Information System (INIS)

    David, G.; Van den Berghe, H.

    1985-01-01

    Chondroitin sulfate represents approximately 15% of the 35 SO 4 -labeled glycosaminoglycans carried by the proteoglycans of the cell surface and of the basolateral secretions of normal mouse mammary epithelial cells in culture. Evidence is provided that these chondroitin sulfate-carrying proteoglycans are hybrid proteoglycans, carrying both chondroitin sulfate and heparan sulfate chains. Complete N-desulfation but limited O-desulfation, by treatment with dimethyl sulfoxide, of the proteoglycans decreased the anionic charge of the chondroitin sulfate-carrying proteoglycans to a greater extent than it decreased the charge of their constituent chondroitin sulfate chains. Partial depolymerization of the heparan sulfate residues of the proteoglycans with nitrous acid or with heparin lyase also reduced the effective molecular radius of the chondroitin sulfate-carrying proteoglycans. The effect of heparin lyase on the chondroitin sulfate-carrying proteoglycans was prevented by treating the proteoglycan fractions with dimethyl sulfoxide, while the effect of nitrous acid on the dimethyl sulfoxide-treated proteoglycans was prevented by acetylation. This occurrence of heparan sulfate-chondroitin sulfate hybrid proteoglycans suggests that the substitution of core proteins by heparan sulfate or chondroitin sulfate chains may not solely be determined by the specific routing of these proteins through distinct chondroitin sulfate and heparan sulfate synthesizing mechanisms. Moreover, regional and temporal changes in pericellular glycosaminoglycan compositions might be due to variable postsynthetic modification of a single gene product

  2. Observational evidence for pollution-influenced selective uptake contributing to biogenic secondary organic aerosols in the southeastern U.S.

    Science.gov (United States)

    Liu, J.; Russell, L. M.; Lee, A. K. Y.; McKinney, K. A.; Surratt, J. D.; Ziemann, P. J.

    2017-08-01

    During the 2013 Southern Oxidant and Aerosol Study, aerosol mass spectrometer measurements of submicron mass and single particles were taken at Look Rock, Tennessee. Their concentrations increased during multiday stagnation events characterized by low wind, little rain, and increased daytime isoprene emissions. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% biogenic secondary organic aerosol (bSOA), with the latter including "sulfate-related bSOA" that correlated to sulfate (r = 0.72) and "nitrate-related bSOA" that correlated to nitrate (r = 0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r > 0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity = 0.97) and the time series correlation (r = 0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants.

  3. Semi-quantitative characterisation of ambient ultrafine aerosols resulting from emissions of coal fired power stations

    International Nuclear Information System (INIS)

    Hinkley, J.T.; Bridgman, H.A.; Buhre, B.J.P.; Gupta, R.P.; Nelson, P.F.; Wall, T.F.

    2008-01-01

    Emissions from coal fired power stations are known to be a significant anthropogenic source of fine atmospheric particles, both through direct primary emissions and secondary formation of sulfate and nitrate from emissions of gaseous precursors. However, there is relatively little information available in the literature regarding the contribution emissions make to the ambient aerosol, particularly in the ultrafine size range. In this study, the contribution of emissions to particles smaller than 0.3 μm in the ambient aerosol was examined at a sampling site 7 km from two large Australian coal fired power stations equipped with fabric filters. A novel approach was employed using conditional sampling based on sulfur dioxide (SO 2 ) as an indicator species, and a relatively new sampler, the TSI Nanometer Aerosol Sampler. Samples were collected on transmission electron microscope (TEM) grids and examined using a combination of TEM imaging and energy dispersive X-ray (EDX) analysis for qualitative chemical analysis. The ultrafine aerosol in low SO 2 conditions was dominated by diesel soot from vehicle emissions, while significant quantities of particles, which were unstable under the electron beam, were observed in the high SO 2 samples. The behaviour of these particles was consistent with literature accounts of sulfate and nitrate species, believed to have been derived from precursor emissions from the power stations. A significant carbon peak was noted in the residues from the evaporated particles, suggesting that some secondary organic aerosol formation may also have been catalysed by these acid seed particles. No primary particulate material was observed in the minus 0.3 μm fraction. The results of this study indicate the contribution of species more commonly associated with gas to particle conversion may be more significant than expected, even close to source

  4. AOD Distributions and Trends of Major Aerosol Species over a Selection of the World's Most Populated Cities Based on the 1st Version of NASA's MERRA Aerosol Reanalysis

    Science.gov (United States)

    Provencal, Simon; Kishcha, Pavel; da Silva, Arlindo M.; Elhacham, Emily; Alpert, Pinhas

    2017-01-01

    NASA recently extended the Modern-Era Retrospective Analysis for Research and Application (MERRA) with an atmospheric aerosol reanalysis which includes five particulate species: sulfate, organic matter, black carbon, mineral dust and sea salt. The MERRA Aerosol Reanalysis (MERRAero) is an innovative tool to study air quality issues around the world for its global and constant coverage and its distinction of aerosol speciation expressed in the form of aerosol optical depth (AOD). The purpose of this manuscript is to apply MERRAero to the study of urban air pollution at the global scale by analyzing the AOD over a period of 13 years (2003-2015) and over a selection of 200 of the world's most populated cities in order to assess the impacts of urbanization, industrialization, air quality regulations and regional transport which affect urban aerosol load. Environmental regulations and the recent global economic recession have helped to decrease the AOD and sulfate aerosols in most cities in North America, Europe and Japan. Rapid industrialization in China over the last two decades resulted in Chinese cities having the highest AOD values in the world. China has nevertheless recently implemented emission control measures which are showing early signs of success in many cities of Southern China where AOD has decreased substantially over the last 13 years. The AOD over South American cities, which is dominated by carbonaceous aerosols, has also decreased over the last decade due to an increase in commodity prices which slowed deforestation activities in the Amazon rainforest. At the opposite, recent urbanization and industrialization in India and Bangladesh resulted in a strong increase of AOD, sulfate and carbonaceous aerosols in most cities of these two countries. The AOD over most cities in Northern Africa and Western Asia changed little over the last decade. Emissions of natural aerosols, which cities in these two regions tend to be mostly composed of, don't tend to

  5. Production of Highly Charged Pharmaceutical Aerosols Using a New Aerosol Induction Charger.

    Science.gov (United States)

    Golshahi, Laleh; Longest, P Worth; Holbrook, Landon; Snead, Jessica; Hindle, Michael

    2015-09-01

    Properly charged particles can be used for effective lung targeting of pharmaceutical aerosols. The objective of this study was to characterize the performance of a new induction charger that operates with a mesh nebulizer for the production of highly charged submicrometer aerosols to bypass the mouth-throat and deliver clinically relevant doses of medications to the lungs. Variables of interest included combinations of model drug (albuterol sulfate) and charging excipient (NaCl) as well as strength of the charging field (1-5 kV/cm). Aerosol charge and size were measured using a modified electrical low pressure impactor system combined with high performance liquid chromatography. At the approximate mass median aerodynamic diameter (MMAD) of the aerosol (~0.4 μm), the induction charge on the particles was an order of magnitude above the field and diffusion charge limit. The nebulization rate was 439.3 ± 42.9 μl/min, which with a 0.1% w/v solution delivered 419.5 ± 34.2 μg of medication per minute. A new correlation was developed to predict particle charge produced by the induction charger. The combination of the aerosol induction charger and predictive correlations will allow for the practical generation and control of charged submicrometer aerosols for targeting deposition within the lungs.

  6. The geochemistry during management of lake acidification caused by the rewetting of sulfuric (pH < 4) acid sulfate soils

    International Nuclear Information System (INIS)

    Mosley, Luke M.; Shand, Paul; Self, Peter; Fitzpatrick, Rob

    2014-01-01

    Highlights: • The dynamic geochemistry of a lake acidification event and its management was assessed. • Sulfate complexes dominated the aqueous metal speciation at low pH. • Iron oxydroxysulfate minerals (schwertmannite, jarosite) were identified. • Aerial additions of limestone to the acidic water slowly returned the pH to near neutral. • Coating of the limestone with gypsum and metal precipitates limited its neutralisation efficiency. - Abstract: Understanding the geochemistry and kinetics of acidification events arising from acid sulfate soils is important to enable effective management and risk assessment. Large-scale exposure and oxidation of acid sulfate soils occurred during a drought in the Lower Lakes (Murray–Darling Basin) of South Australia. We examined the geochemical changes that occurred in one region (Boggy Lake) that experienced surface water acidification and was subsequently neutralised via aerial limestone (CaCO 3 ) dosing and dilution via natural lake refill. Very low pH (< 3) and high concentrations (≈10–1000 mg/L Fe, Al, Mn) of dissolved metals were initially found in surface water. The water chemistry exhibited pH-dependent enhancement of constituents typically associated with acid sulfate soils (SO 4 , Al and Fe). Geochemical speciation calculations indicated that most (60–80%) of the acidity was present as dissolved metal-sulfate complexes at low pH. X-ray diffraction (XRD) analyses showed that the orange-brown precipitates present after an initial limestone dosing were secondary oxyhydroxysulfate minerals (schwertmannite, jarosite). Further limestone dosing resulted in neutralisation of the pH, reduction in dissolved metal concentrations, dissolution of jarosite and schwertmannite precipitates, and formation of other metal oxyhydroxide phases. The results were consistent with a pE-pH diagram constructed for metal-sulfur geochemistry. Assessment of the measured and simulated (using PHREEQC) pH and Ca/Cl ratio during

  7. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Fine resolution atmospheric sulfate model driven by operational meteorological data: Comparison with observations

    International Nuclear Information System (INIS)

    Benkovitz, C.M.; Schwartz, S.E.; Berkowitz, C.M.; Easter, R.C.

    1993-09-01

    The hypothesis that anthropogenic sulfur aerosol influences clear-sky and cloud albedo and can thus influence climate has been advanced by several investigators; current global-average climate forcing is estimated to be of comparable magnitude, but opposite sign, to longwave forcing by anthropogenic greenhouse gases. The high space and time variability of sulfate concentrations and column aerosol burdens have been established by observational data; however, geographic and time coverage provided by data from surface monitoring networks is very limited. Consistent regional and global estimates of sulfate aerosol loading, and the contributions to this loading from different sources can be obtained only by modeling studies. Here we describe a sub-hemispheric to global-scale Eulerian transport and transformation model for atmospheric sulfate and its precursors, driven by operational meteorological data, and report results of calculations for October, 1986 for the North Atlantic and adjacent continental regions. The model, which is based on the Global Chemistry Model uses meteorological data from the 6-hour forecast model of the European Center for Medium-Range Weather Forecast to calculate transport and transformation of sulfur emissions. Time- and location-dependent dry deposition velocities were estimated using the methodology of Wesely and colleagues. Chemical reactions includes gaseous oxidation of SO 2 and DMS by OH, and aqueous oxidation of SO 2 by H 2 O 2 and O 3 . Anthropogenic emissions were from the NAPAP and EMEP 1985 inventories and biogenic emissions based on Bates et al. Calculated sulfate concentrations and column burdens exhibit high variability on spatial scale of hundreds of km and temporal scale of days. Calculated daily average sulfate concentrations closely reproduce observed concentrations at locations widespread over the model domain

  9. Assessment of sand quality on concrete performance : examination of acidic and sulfate/sulfide-bearing sands.

    Science.gov (United States)

    2014-12-01

    The purpose of this research is to examine how the presence of sulfide- and sulfate-containing : minerals in acidic aggregates may affect the properties of mortar and concrete. Analyses were : performed to compare two sands from a deposit in the Geor...

  10. 21 CFR 184.1261 - Copper sulfate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of a...

  11. Could aerosol emissions be used for regional heat wave mitigation?

    Directory of Open Access Journals (Sweden)

    D. N. Bernstein

    2013-07-01

    Full Text Available Geoengineering applications by injection of sulfate aerosols into the stratosphere are under consideration as a measure of last resort to counter global warming. Here a potential regional-scale application to offset the impacts of heat waves is critically examined. Using the Weather Research and Forecasting model with fully coupled chemistry (WRF-Chem, the effect of regional-scale sulfate aerosol emission over California in each of two days of the July 2006 heat wave is used to quantify potential reductions in surface temperature as a function of emission rates in a layer at 12 km altitude. Local meteorological factors yield geographical differences in surface air temperature sensitivity. For emission rates of approximately 30 μg m−2 s−1 of sulfate aerosols (with standard WRF-Chem size distribution over the region, temperature decreases of around 7 °C result during the middle part of the day over the Central Valley, one of the areas hardest hit by the heat wave. Regions more ventilated with oceanic air such as Los Angeles have slightly smaller reductions. The length of the hottest part of the day is also reduced. Advection effects on the aerosol cloud must be more carefully forecast for smaller injection regions. Verification of the impacts could be done via measurements of differences in reflected and surface downward shortwave. Such regional geoengineering applications with specific near-term target effects but smaller cost and side effects could potentially provide a means of testing larger scale applications. However, design considerations for regional applications, such as a preference for injection at a level of relatively low wind speed, differ from those for global applications. The size of the required injections and the necessity of injection close to the target region raise substantial concerns. The evaluation of this regional-scale application is thus consistent with global model evaluations, emphasizing that mitigation via

  12. Photochemical aging of aerosol particles in different air masses arriving at Baengnyeong Island, Korea

    Science.gov (United States)

    Kang, Eunha; Lee, Meehye; Brune, William H.; Lee, Taehyoung; Park, Taehyun; Ahn, Joonyoung; Shang, Xiaona

    2018-05-01

    Atmospheric aerosol particles are a serious health risk, especially in regions like East Asia. We investigated the photochemical aging of ambient aerosols using a potential aerosol mass (PAM) reactor at Baengnyeong Island in the Yellow Sea during 4-12 August 2011. The size distributions and chemical compositions of aerosol particles were measured alternately every 6 min from the ambient air or through the highly oxidizing environment of a potential aerosol mass (PAM) reactor. Particle size and chemical composition were measured by using the combination of a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Inside the PAM reactor, O3 and OH levels were equivalent to 4.6 days of integrated OH exposure at typical atmospheric conditions. Two types of air masses were distinguished on the basis of the chemical composition and the degree of aging: air transported from China, which was more aged with a higher sulfate concentration and O : C ratio, and the air transported across the Korean Peninsula, which was less aged with more organics than sulfate and a lower O : C ratio. For both episodes, the particulate sulfate mass concentration increased in the 200-400 nm size range when sampled through the PAM reactor. A decrease in organics was responsible for the loss of mass concentration in 100-200 nm particles when sampled through the PAM reactor for the organics-dominated episode. This loss was especially evident for the m/z 43 component, which represents less oxidized organics. The m/z 44 component, which represents further oxidized organics, increased with a shift toward larger sizes for both episodes. It is not possible to quantify the maximum possible organic mass concentration for either episode because only one OH exposure of 4.6 days was used, but it is clear that SO2 was a primary precursor of secondary aerosol in northeast Asia, especially during long-range transport from China. In addition

  13. Effect of inorganic salts on the volatility of organic acids.

    Science.gov (United States)

    Häkkinen, Silja A K; McNeill, V Faye; Riipinen, Ilona

    2014-12-02

    Particulate phase reactions between organic and inorganic compounds may significantly alter aerosol chemical properties, for example, by suppressing particle volatility. Here, chemical processing upon drying of aerosols comprised of organic (acetic, oxalic, succinic, or citric) acid/monovalent inorganic salt mixtures was assessed by measuring the evaporation of the organic acid molecules from the mixture using a novel approach combining a chemical ionization mass spectrometer coupled with a heated flow tube inlet (TPD-CIMS) with kinetic model calculations. For reference, the volatility, i.e. saturation vapor pressure and vaporization enthalpy, of the pure succinic and oxalic acids was also determined and found to be in agreement with previous literature. Comparison between the kinetic model and experimental data suggests significant particle phase processing forming low-volatility material such as organic salts. The results were similar for both ammonium sulfate and sodium chloride mixtures, and relatively more processing was observed with low initial aerosol organic molar fractions. The magnitude of low-volatility organic material formation at an atmospherically relevant pH range indicates that the observed phenomenon is not only significant in laboratory conditions but is also of direct atmospheric relevance.

  14. Prediction of health effects of cross-border atmospheric pollutants using an aerosol forecast model.

    Science.gov (United States)

    Onishi, Kazunari; Sekiyama, Tsuyoshi Thomas; Nojima, Masanori; Kurosaki, Yasunori; Fujitani, Yusuke; Otani, Shinji; Maki, Takashi; Shinoda, Masato; Kurozawa, Youichi; Yamagata, Zentaro

    2018-08-01

    Health effects of cross-border air pollutants and Asian dust are of significant concern in Japan. Currently, models predicting the arrival of aerosols have not investigated the association between arrival predictions and health effects. We investigated the association between subjective health symptoms and unreleased aerosol data from the Model of Aerosol Species in the Global Atmosphere (MASINGAR) acquired from the Japan Meteorological Agency, with the objective of ascertaining if these data could be applied to predicting health effects. Subjective symptom scores were collected via self-administered questionnaires and, along with modeled surface aerosol concentration data, were used to conduct a risk evaluation using generalized estimating equations between October and November 2011. Altogether, 29 individuals provided 1670 responses. Spearman's correlation coefficients were determined for the relationship between the proportion of the participants reporting the maximum score of two or more for each symptom and the surface concentrations for each considered aerosol species calculated using MASINGAR; the coefficients showed significant intermediate correlations between surface sulfate aerosol concentration and respiratory, throat, and fever symptoms (R = 0.557, 0.454, and 0.470, respectively; p < 0.01). In the general estimation equation (logit link) analyses, a significant linear association of surface sulfate aerosol concentration, with an endpoint determined by reported respiratory symptom scores of two or more, was observed (P trend = 0.001, odds ratio [OR] of the highest quartile [Q4] vs. the lowest [Q1] = 5.31, 95% CI = 2.18 to 12.96), with adjustment for potential confounding. The surface sulfate aerosol concentration was also associated with throat and fever symptoms. In conclusion, our findings suggest that modeled data are potentially useful for predicting health risks of cross-border aerosol arrivals. Copyright © 2018 Elsevier Ltd

  15. Mixing state of ambient aerosols during different fog-haze pollution episodes in the Yangtze River Delta, China

    Science.gov (United States)

    Hu, Rui; Wang, Honglei; Yin, Yan; Chen, Kui; Zhu, Bin; Zhang, Zefeng; Kang, Hui; Shen, Lijuan

    2018-04-01

    The mixing state of aerosol particles were investigated using a single particle aerosol mass spectrometer (SPAMS) during a regional fog-haze episode in the Yangtze River Delta (YRD) on 16-28 Dec., 2015. The aerosols were analyzed and clustered into 12 classes: aged elemental carbon (Aged-EC), internally mixed organics and elemental carbon (ECOC), organic carbon (OC), Biomass, Amine, Ammonium, Na-K, V-rich, Pb-rich, Cu-rich, Fe-rich and Dust. Results showed that particles in short-term rainfalls mixed with more nitrate and oxidized organics, while they mixed with more ammonium and sulfate in long-term rainfall. Due to anthropogenic activities, stronger winds and solar radiation, the particle counts increased and the size ranges of particles broadened in haze. Carbonaceous particles and Na-K mixed with enhanced secondary species during haze, and obviously were more acidic, especially for the ones with a size range of 0.6-1.2 μm. For local and long-range transported pollution, OC had distinct size distributions while the changes of ECOC were uniform. The secondary formation of ECOC contributed significantly in local pollution and affected much smaller particles (as small as 0.5 μm) in long-range transported pollution. And long-range transported pollution was more helpful for the growth of OC. Particles mixed with more chloride and nitrate/sulfate in local/long-range transported pollution.

  16. 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 (SO 3 -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.

  17. Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

    Science.gov (United States)

    Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; Berg, Larry K.; Fast, Jerome D.; Easter, Richard C.; Shrivastava, Manish; Thomas, Jennie L.

    2017-10-01

    In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain-Fritsch + Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

  18. Extraction of beryllium sulfate by a long chain amine; Extraction du sulfate de beryllium par une amine a longue chaine

    Energy Technology Data Exchange (ETDEWEB)

    Etaix, E.S. [Commissariat a l' Energie Atomique, Fontenay-Aux-Roses (France). Centre d' Etudes Nucleaires

    1968-06-01

    The extraction of sulfuric acid in aqueous solution by a primary amine in benzene solution, 3-9 (diethyl) - 6-amino tri-decane (D.E.T. ) - i.e., with American nomenclature 1-3 (ethyl-pentyl) - 4-ethyl-octyl amine (E.P.O.) - has made it possible to calculate the formation constants of alkyl-ammonium sulfate and acid sulfate. The formula of the beryllium and alkyl-ammonium sulfate complex formed in benzene has next been determined, for various initial acidity of the aqueous solution. Lastly, evidence has been given of negatively charged complexes of beryllium and sulfate in aqueous solution, through the dependence of the aqueous sulfate ions concentration upon beryllium extraction. The formation constant of these anionic complexes has been evaluated. (author) [French] L'etude de l'extraction de l'acide sulfurique en solution aqueuse par une amine primaire en solution dans le benzene, le diethyl-3,9 amino-6 tridecane (D.E.T.) - autre nom americain 1-3 (ethylpentyl) - 4-ethyloctylamine (E.P.O.) a permis de calculer les constantes de formation du sulfate et de l'hydrogenosulfate d'alkyl-ammonium. La formule du complexe de sulfate de beryllium et d'alkyl-ammonium forme en solution benzenique a ete ensuite determinee pour diverses acidites initiales de la solution aqueuse. Enfin, l'influence de la concentration des ions sulfate de la phase aqueuse sur l'extraction du beryllium a mis en evidence la formation en solution aqueuse de complexes anioniques de sulfate et de beryllium dont la constante de formation a ete evaluee. (auteur)

  19. Extraction of beryllium sulfate by a long chain amine; Extraction du sulfate de beryllium par une amine a longue chaine

    Energy Technology Data Exchange (ETDEWEB)

    Etaix, E S [Commissariat a l' Energie Atomique, Fontenay-Aux-Roses (France). Centre d' Etudes Nucleaires

    1968-06-01

    The extraction of sulfuric acid in aqueous solution by a primary amine in benzene solution, 3-9 (diethyl) - 6-amino tri-decane (D.E.T. ) - i.e., with American nomenclature 1-3 (ethyl-pentyl) - 4-ethyl-octyl amine (E.P.O.) - has made it possible to calculate the formation constants of alkyl-ammonium sulfate and acid sulfate. The formula of the beryllium and alkyl-ammonium sulfate complex formed in benzene has next been determined, for various initial acidity of the aqueous solution. Lastly, evidence has been given of negatively charged complexes of beryllium and sulfate in aqueous solution, through the dependence of the aqueous sulfate ions concentration upon beryllium extraction. The formation constant of these anionic complexes has been evaluated. (author) [French] L'etude de l'extraction de l'acide sulfurique en solution aqueuse par une amine primaire en solution dans le benzene, le diethyl-3,9 amino-6 tridecane (D.E.T.) - autre nom americain 1-3 (ethylpentyl) - 4-ethyloctylamine (E.P.O.) a permis de calculer les constantes de formation du sulfate et de l'hydrogenosulfate d'alkyl-ammonium. La formule du complexe de sulfate de beryllium et d'alkyl-ammonium forme en solution benzenique a ete ensuite determinee pour diverses acidites initiales de la solution aqueuse. Enfin, l'influence de la concentration des ions sulfate de la phase aqueuse sur l'extraction du beryllium a mis en evidence la formation en solution aqueuse de complexes anioniques de sulfate et de beryllium dont la constante de formation a ete evaluee. (auteur)

  20. Dry deposition of sulfate to Quercus rubra and Liriodendron tulipifera foliage

    International Nuclear Information System (INIS)

    Vandenberg, J.J.

    1987-01-01

    Estimates were made of the rate of dry deposition to red oak (Quercus rubra) and tulip poplar (Liriodendron tulipifera) foliage. In the laboratory, radioactive ammonium sulfate aerosols were generated in an exposure chamber. These aerosols were dry deposited onto leaves that were sequentially washed to examine the efficacy of washing procedures in removal of surface deposits. Over 90% of dry deposited sulfate was removed after a 30 second wash duration. Laboratory procedures also estimated the magnitude of foliar sulfur that leached into leaf wash solutions. The majority of laboratory leaves demonstrated no leaching of sulfur from the internal pool. However, some leaves showed significant sulfur leaching. It was concluded that leaching of internal sulfur was highly leaf specific. This indicated that each leaf used in field experiments needed to be individually examined for leaching

  1. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Characterization of distinct Arctic aerosol accumulation modes and their sources

    Science.gov (United States)

    Lange, R.; Dall'Osto, M.; Skov, H.; Nøjgaard, J. K.; Nielsen, I. E.; Beddows, D. C. S.; Simo, R.; Harrison, R. M.; Massling, A.

    2018-06-01

    In this work we use cluster analysis of long term particle size distribution data to expand an array of different shorter term atmospheric measurements, thereby gaining insights into longer term patterns and properties of Arctic aerosol. Measurements of aerosol number size distributions (9-915 nm) were conducted at Villum Research Station (VRS), Station Nord in North Greenland during a 5 year record (2012-2016). Alongside this, measurements of aerosol composition, meteorological parameters, gaseous compounds and cloud condensation nuclei (CCN) activity were performed during different shorter occasions. K-means clustering analysis of particle number size distributions on daily basis identified several clusters. Clusters of accumulation mode aerosols (main size modes > 100 nm) accounted for 56% of the total aerosol during the sampling period (89-91% during February-April, 1-3% during June-August). By association to chemical composition, cloud condensation nuclei properties, and meteorological variables, three typical accumulation mode aerosol clusters were identified: Haze (32% of the time), Bimodal (14%) and Aged (6%). In brief: (1) Haze accumulation mode aerosol shows a single mode at 150 nm, peaking in February-April, with highest loadings of sulfate and black carbon concentrations. (2) Accumulation mode Bimodal aerosol shows two modes, at 38 nm and 150 nm, peaking in June-August, with the highest ratio of organics to sulfate concentrations. (3) Aged accumulation mode aerosol shows a single mode at 213 nm, peaking in September-October and is associated with cloudy and humid weather conditions during autumn. The three aerosol clusters were considered alongside CCN concentrations. We suggest that organic compounds, that are likely marine biogenic in nature, greatly influence the Bimodal cluster and contribute significantly to its CCN activity. This stresses the importance of better characterizing the marine ecosystem and the aerosol-mediated climate effects in the

  3. The influence of different black carbon and sulfate mixing methods on their optical and radiative properties

    Science.gov (United States)

    Zhang, Hua; Zhou, Chen; Wang, Zhili; Zhao, Shuyun; Li, Jiangnan

    2015-08-01

    Three different internal mixing methods (Core-Shell, Maxwell-Garnett, and Bruggeman) and one external mixing method are used to study the impact of mixing methods of black carbon (BC) with sulfate aerosol on their optical properties, radiative flux, and heating rate. The optical properties of a mixture of BC and sulfate aerosol particles are considered for three typical bands. The results show that mixing methods, the volume ratio of BC to sulfate, and relative humidity have a strong influence on the optical properties of mixed aerosols. Compared to internal mixing, external mixing underestimates the particle mass absorption coefficient by 20-70% and the particle mass scattering coefficient by up to 50%, whereas it overestimates the particle single scattering albedo by 20-50% in most cases. However, the asymmetry parameter is strongly sensitive to the equivalent particle radius, but is only weakly sensitive to the different mixing methods. Of the internal methods, there is less than 2% difference in all optical properties between the Maxwell-Garnett and Bruggeman methods in all bands; however, the differences between the Core-Shell and Maxwell-Garnett/Bruggeman methods are usually larger than 15% in the ultraviolet and visible bands. A sensitivity test is conducted with the Beijing Climate Center Radiation transfer model (BCC-RAD) using a simulated BC concentration that is typical of east-central China and a sulfate volume ratio of 75%. The results show that the internal mixing methods could reduce the radiative flux more effectively because they produce a higher absorption. The annual mean instantaneous radiative force due to BC-sulfate aerosol is about -3.18 W/m2 for the external method and -6.91 W/m2 for the internal methods at the surface, and -3.03/-1.56/-1.85 W/m2 for the external/Core-Shell/(Maxwell-Garnett/Bruggeman) methods, respectively, at the tropopause.

  4. 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.

  5. Sulfated steroid-amino acid conjugates from the Irish marine sponge Polymastia boletiformis.

    Science.gov (United States)

    Smyrniotopoulos, Vangelis; Rae, Margaret; Soldatou, Sylvia; Ding, Yuanqing; Wolff, Carsten W; McCormack, Grace; Coleman, Christina M; Ferreira, Daneel; Tasdemir, Deniz

    2015-03-24

    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.

  6. 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...

  7. Metabolic interactions in methanogenic and sulfate-reducing bioreactors.

    Science.gov (United States)

    Stams, A J M; Plugge, C M; de Bok, F A M; van Houten, B H G W; Lens, P; Dijkman, H; Weijma, J

    2005-01-01

    In environments where the amount of electron acceptors is insufficient for complete breakdown of organic matter, methane is formed as the major reduced end product. In such methanogenic environments organic acids are degraded by syntrophic consortia of acetogenic bacteria and methanogenic archaea. Hydrogen consumption by methanogens is essential for acetogenic bacteria to convert organic acids to acetate and hydrogen. Several syntrophic cocultures growing on propionate and butyrate have been described. These syntrophic fatty acid-degrading consortia are affected by the presence of sulfate. When sulfate is present sulfate-reducing bacteria compete with methanogenic archaea for hydrogen and acetate, and with acetogenic bacteria for propionate and butyrate. Sulfate-reducing bacteria easily outcompete methanogens for hydrogen, but the presence of acetate as carbon source may influence the outcome of the competition. By contrast, acetoclastic methanogens can compete reasonably well with acetate-degrading sulfate reducers. Sulfate-reducing bacteria grow much faster on propionate and butyrate than syntrophic consortia.

  8. Activation of Recombinantly Expressed l-Amino Acid Oxidase from Rhizoctonia solani by Sodium Dodecyl Sulfate

    Directory of Open Access Journals (Sweden)

    Katharina Hahn

    2017-12-01

    Full Text Available l-Amino acid oxidases (l-AAO catalyze the oxidative deamination of l-amino acids to the corresponding α-keto acids. The non-covalently bound cofactor FAD is reoxidized by oxygen under formation of hydrogen peroxide. We expressed an active l-AAO from the fungus Rhizoctonia solani as a fusion protein in E. coli. Treatment with small amounts of the detergent sodium dodecyl sulfate (SDS stimulated the activity of the enzyme strongly. Here, we investigated whether other detergents and amphiphilic molecules activate 9His-rsLAAO1. We found that 9His-rsLAAO1 was also activated by sodium tetradecyl sulfate. Other detergents and fatty acids were not effective. Moreover, effects of SDS on the oligomerization state and the protein structure were analyzed. Native and SDS-activated 9His-rsLAAO1 behaved as dimers by size-exclusion chromatography. SDS treatment induced an increase in hydrodynamic radius as observed by size-exclusion chromatography and dynamic light scattering. The activated enzyme showed accelerated thermal inactivation and an exposure of additional protease sites. Changes in tryptophan fluorescence point to a more hydrophilic environment. Moreover, FAD fluorescence increased and a lower concentration of sulfites was sufficient to form adducts with FAD. Taken together, these data point towards a more open conformation of SDS-activated l-amino acid oxidase facilitating access to the active site.

  9. Standard practice for monitoring atmospheric SO2 using the sulfation plate technique

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1997-01-01

    1.1 This practice covers a weighted average effective SO2 level for a 30-day interval through the use of the sulfation plate method, a technique for estimating the effective SO2 content of the atmosphere, and especially with regard to the atmospheric corrosion of stationary structures or panels. This practice is aimed at determining SO2 levels rather than sulfuric acid aerosol or acid precipitation. 1.2 The results of this practice correlate approximately with volumetric SO2 concentrations, although the presence of dew or condensed moisture tends to enhance the capture of SO2 into the plate. 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  10. Marine Emissions and Atmospheric Processing Influence Aerosol Mixing States in the Bering Strait and Chukchi Sea

    Science.gov (United States)

    Kirpes, R.; Rodriguez, B.; Kim, S.; Park, K.; China, S.; Laskin, A.; Pratt, K.

    2017-12-01

    The Arctic region is rapidly changing due to sea ice loss and increasing oil/gas development and shipping activity. These changes influence aerosol sources and composition, resulting in complex aerosol-cloud-climate feedbacks. Atmospheric particles were collected aboard the R/V Araon in July-August 2016 in the Alaskan Arctic along the Bering Strait and Chukchi Sea. Offline analysis of individual particles by microscopic and spectroscopic techniques provided information on particle size, morphology, and chemical composition. Sea spray aerosol (SSA) and organic aerosol (OA) particles were the most commonly observed particle types, and sulfate was internally mixed with both SSA and OA. Evidence of multiphase sea spray aerosol reactions was observed, with varying degrees of chlorine depletion observed along the cruise. Notably, atmospherically processed SSA, completely depleted in chlorine, and internally mixed organic and sulfate particles, were observed in samples influenced by the central Arctic Ocean. Changes in particle composition due to fog processing were also investigated. Due to the changing aerosol sources and atmospheric processes in the Arctic region, it is crucial to understand aerosol composition in order to predict climate impacts.

  11. Mine Waste Technology Program. In Situ Source Control Of Acid Generation Using Sulfate-Reducing Bacteria

    Science.gov (United States)

    This report summarizes the results of the Mine Waste Technology Program (MWTP) Activity III, Project 3, In Situ Source Control of Acid Generation Using Sulfate-Reducing Bacteria, funded by the U.S. Environmental Protection Agency (EPA) and jointly administered by EPA and the U.S....

  12. AOD distributions and trends of major aerosol species over a selection of the world’s most populated cities based on the 1st Version of NASA’s MERRA Aerosol Reanalysis

    Science.gov (United States)

    Provençal, Simon; Kishcha, Pavel; da Silva, Arlindo M.; Elhacham, Emily; Alpert, Pinhas

    2018-01-01

    NASA recently extended the Modern-Era Retrospective Analysis for Research and Application (MERRA) with an atmospheric aerosol reanalysis which includes five particulate species: sulfate, organic matter, black carbon, mineral dust and sea salt. The MERRA Aerosol Reanalysis (MERRAero) is an innovative tool to study air quality issues around the world for its global and constant coverage and its distinction of aerosol speciation expressed in the form of aerosol optical depth (AOD). The purpose of this manuscript is to apply MERRAero to the study of urban air pollution at the global scale by analyzing the AOD over a period of 13 years (2003–2015) and over a selection of 200 of the world’s most populated cities in order to assess the impacts of urbanization, industrialization, air quality regulations and regional transport which affect urban aerosol load. Environmental regulations and the recent global economic recession have helped to decrease the AOD and sulfate aerosols in most cities in North America, Europe and Japan. Rapid industrialization in China over the last two decades resulted in Chinese cities having the highest AOD values in the world. China has nevertheless recently implemented emission control measures which are showing early signs of success in many cities of Southern China where AOD has decreased substantially over the last 13 years. The AOD over South American cities, which is dominated by carbonaceous aerosols, has also decreased over the last decade due to an increase in commodity prices which slowed deforestation activities in the Amazon rainforest. At the opposite, recent urbanization and industrialization in India and Bangladesh resulted in a strong increase of AOD, sulfate and carbonaceous aerosols in most cities of these two countries. The AOD over most cities in Northern Africa and Western Asia changed little over the last decade. Emissions of natural aerosols, which cities in these two regions tend to be mostly composed of, don’t tend

  13. TEM study of soot, organic aerosol, and sea-salt particles collected during CalNex

    Science.gov (United States)

    Adachi, K.; Buseck, P. R.

    2010-12-01

    Anthropogenic aerosol particles are emitted in abundance from megacities. Those particles can have important effects on both human health and climate. In this study, aerosol particles having aerodynamic diameters between 50 and 300 nm were collected during the CalNex campaign at the Pasadena ground site from May 15 to June 15, 2010, ~15 km northeast of downtown Los Angeles. The samples were analyzed using transmission electron microscopes (TEMs) to characterize particle shapes and compositions. Most samples are dominated by soot, organic aerosol (OA), sulfate, sea salt, or combinations thereof. Sizes and amounts of OA particles increased during the afternoons, and most soot particles were internally mixed with OA and sulfate in the afternoons. The proportion of soot to other material in individual particles increased and soot particles were more compact during the nights and early mornings. Sea-salt particles were commonly internally mixed with other materials. They have high Na contents with lesser N, Mg, S, K, and Ca and almost no Cl, suggesting that the Cl was replaced by sulfate or nitrate in the atmosphere. There is less OA and more sea salt and sulfate in the CalNex samples than in the samples from Mexico City that were collected during the MILAGRO campaign. Our study indicates that compositions of internally mixed aerosol particles and shapes of soot particles change significantly within a day. These changes probably influence the estimates of their effects on human health and climate.

  14. Extraction of beryllium sulfate by a long chain amine

    International Nuclear Information System (INIS)

    Etaix, E.S.

    1968-01-01

    The extraction of sulfuric acid in aqueous solution by a primary amine in benzene solution, 3-9 (diethyl) - 6-amino tri-decane (D.E.T. ) - i.e., with American nomenclature 1-3 (ethyl-pentyl) - 4-ethyl-octyl amine (E.P.O.) - has made it possible to calculate the formation constants of alkyl-ammonium sulfate and acid sulfate. The formula of the beryllium and alkyl-ammonium sulfate complex formed in benzene has next been determined, for various initial acidity of the aqueous solution. Lastly, evidence has been given of negatively charged complexes of beryllium and sulfate in aqueous solution, through the dependence of the aqueous sulfate ions concentration upon beryllium extraction. The formation constant of these anionic complexes has been evaluated. (author) [fr

  15. Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT): Overview of a wintertime air chemistry field study in the front range urban corridor of Colorado

    Science.gov (United States)

    Brown, Steven S.; Thornton, Joel A.; Keene, William C.; Pszenny, Alexander A. P.; Sive, Barkley C.; Dubé, William P.; Wagner, Nicholas L.; Young, Cora J.; Riedel, Theran P.; Roberts, James M.; VandenBoer, Trevor C.; Bahreini, Roya; Öztürk, Fatma; Middlebrook, Ann M.; Kim, Saewung; Hübler, Gerhard; Wolfe, Daniel E.

    2013-07-01

    The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) field experiment took place during late winter, 2011, at a site 33 km north of Denver, Colorado. The study included fixed-height measurements of aerosols, soluble trace gases, and volatile organic compounds near surface level, as well as vertically resolved measurements of nitrogen oxides, aerosol composition, soluble gas-phase acids, and halogen species from 3 to 270 m above ground level. There were 1928 individual profiles during the three-week campaign to characterize trace gas and aerosol distributions in the lower levels of the boundary layer. Nitrate and ammonium dominated the ionic composition of aerosols and originated primarily from local or regional sources. Sulfate and organic matter were also significant and were associated primarily with longer-range transport to the region. Aerosol chloride was associated primarily with supermicron size fractions and was always present in excess of gas-phase chlorine compounds. The nighttime radical reservoirs, nitryl chloride, ClNO2, and nitrous acid, HONO, were both consistently present in nighttime urban air. Nitryl chloride was especially pronounced in plumes from large point sources sampled aloft at night. Nitrous acid was typically most concentrated near the ground surface and was the dominant contributor (80%) to diurnally averaged primary OH radical production in near-surface air. Large observed mixing ratios of light alkanes, both in near-surface air and aloft, were attributable to local emissions from oil and gas activities.

  16. Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

    Directory of Open Access Journals (Sweden)

    Y.-L. Sun

    2011-02-01

    analysis of NOA (5.8% of OA presents evidence that organic nitrogen species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving both acid-base chemistry and photochemistry. In addition, analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.

  17. Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

    Directory of Open Access Journals (Sweden)

    D. R. Worton

    2011-10-01

    (>75%. The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1% of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NOx enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site.

  18. Composite study of aerosol export events from East Asia and North America

    Directory of Open Access Journals (Sweden)

    Y. Luan

    2013-02-01

    Full Text Available We use satellite observations of aerosol optical depth (AOD from the Moderate Resolution Imaging Spectrometer (MODIS together with the GEOS-Chem global chemical transport model to contrast export of aerosols from East Asia and North America during 2004–2010. The GEOS-Chem model reproduces the spatial distribution and temporal variations of Asian aerosol outflow generally well, although a low bias (−30% is found in the model fine mode AOD, particularly during summer. We use the model to identify 244 aerosol pollution export events from E. Asia and 251 export events from N. America over our 7-year study period. When these events are composited by season, we find that the AOD in the outflow is enhanced by 50–100% relative to seasonal mean values. The composite Asian plume splits into one branch going poleward to the Arctic in 3–4 days, with the other crossing the Pacific Ocean in 6–8 days. A fraction of the aerosols is trapped in the subtropical Pacific High during spring and summer. The N. American plume travels to the northeast Atlantic, reaching Europe after 4–5 days. Part of the composite plume turns anticyclonically in the Azores High, where it slowly decays. Both the Asian and N. American export events are favored by a dipole structure in sea-level pressure anomalies, associated with mid-latitude cyclone activity over the respective source regions. This dipole structure during outflow events is a strong feature for all seasons except summer, when convection becomes more important. The observed AOD in the E. Asian outflow exhibits stronger seasonality, with a spring maximum, than the N. American outflow, with a broad spring/summer maximum. The large spring AOD in the Asian outflow is the result of enhanced sulfate and dust aerosol concentrations, but is also due to a larger export efficiency of sulfate and SO2 from the Asian boundary layer relative to the N. American boundary layer. While the N. American sulfate outflow

  19. The distribution of n-caprylic acid between organic solvents and aqueous sodium sulfate solution

    International Nuclear Information System (INIS)

    Gloe, K.; Muehl, P.; Kholkin, A.I.; Gindin, L.M.

    1981-01-01

    The distribution of 14 C-labelled n-caprylic acid between n-decane, benzene, isoamyl acetate, diisopropyl ketone, isoamyl alcohol and an aqueous 0.6 molar sodium sulfate solution was studied. The distribution constants and the dimerisation constants were determined for the reactions HRsub((w)) reversible HRsub((org)) and 2 HRsub((org)) reversible (HR)sub(2(org)), respectively. Both the effect of the solvent on the acid distribution and the importance of such studies for the interpretation of liquid-liquid extraction equilibria are discussed. (author)

  20. Individual aerosol particles in and below clouds along a Mt. Fuji slope: Modification of sea-salt-containing particles by in-cloud processing

    Science.gov (United States)

    Ueda, S.; Hirose, Y.; Miura, K.; Okochi, H.

    2014-02-01

    Sizes and compositions of atmospheric aerosol particles can be altered by in-cloud processing by absorption/adsorption of gaseous and particulate materials and drying of aerosol particles that were formerly activated as cloud condensation nuclei. To elucidate differences of aerosol particles before and after in-cloud processing, aerosols were observed along a slope of Mt. Fuji, Japan (3776 m a.s.l.) during the summer in 2011 and 2012 using a portable laser particle counter (LPC) and an aerosol sampler. Aerosol samples for analyses of elemental compositions were obtained using a cascade impactor at top-of-cloud, in-cloud, and below-cloud altitudes. To investigate composition changes via in-cloud processing, individual particles (0.5-2 μm diameter) of samples from five cases (days) collected at different altitudes under similar backward air mass trajectory conditions were analyzed using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray analyzer. For most cases (four cases), most particles at all altitudes mainly comprised sea salts: mainly Na with some S and/or Cl. Of those, in two cases, sea-salt-containing particles with Cl were found in below-cloud samples, although sea-salt-containing particles in top-of-cloud samples did not contain Cl. This result suggests that Cl in the sea salt was displaced by other cloud components. In the other two cases, sea-salt-containing particles on samples at all altitudes were without Cl. However, molar ratios of S to Na (S/Na) of the sea-salt-containing particles of top-of-cloud samples were higher than those of below-cloud samples, suggesting that sulfuric acid or sulfate was added to sea-salt-containing particles after complete displacement of Cl by absorption of SO2 or coagulation with sulfate. The additional volume of sulfuric acid in clouds for the two cases was estimated using the observed S/Na values of sea-salt-containing particles. The estimation revealed that size changes by in

  1. Online Simulations of Global Aerosol Distributions in the NASA GEOS-4 Model and Comparisons to Satellite and Ground-Based Aerosol Optical Depth

    Science.gov (United States)

    Colarco, Peter; daSilva, Arlindo; Chin, Mian; Diehl, Thomas

    2010-01-01

    We have implemented a module for tropospheric aerosols (GO CART) online in the NASA Goddard Earth Observing System version 4 model and simulated global aerosol distributions for the period 2000-2006. The new online system offers several advantages over the previous offline version, providing a platform for aerosol data assimilation, aerosol-chemistry-climate interaction studies, and short-range chemical weather forecasting and climate prediction. We introduce as well a methodology for sampling model output consistently with satellite aerosol optical thickness (AOT) retrievals to facilitate model-satellite comparison. Our results are similar to the offline GOCART model and to the models participating in the AeroCom intercomparison. The simulated AOT has similar seasonal and regional variability and magnitude to Aerosol Robotic Network (AERONET), Moderate Resolution Imaging Spectroradiometer, and Multiangle Imaging Spectroradiometer observations. The model AOT and Angstrom parameter are consistently low relative to AERONET in biomass-burning-dominated regions, where emissions appear to be underestimated, consistent with the results of the offline GOCART model. In contrast, the model AOT is biased high in sulfate-dominated regions of North America and Europe. Our model-satellite comparison methodology shows that diurnal variability in aerosol loading is unimportant compared to sampling the model where the satellite has cloud-free observations, particularly in sulfate-dominated regions. Simulated sea salt burden and optical thickness are high by a factor of 2-3 relative to other models, and agreement between model and satellite over-ocean AOT is improved by reducing the model sea salt burden by a factor of 2. The best agreement in both AOT magnitude and variability occurs immediately downwind of the Saharan dust plume.

  2. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Thermodynamic data for modeling acid mine drainage problems: compilation and estimation of data for selected soluble iron-sulfate minerals

    Science.gov (United States)

    Hemingway, Bruch S.; Seal, Robert R.; Chou, I-Ming

    2002-01-01

    Enthalpy of formation, Gibbs energy of formation, and entropy values have been compiled from the literature for the hydrated ferrous sulfate minerals melanterite, rozenite, and szomolnokite, and a variety of other hydrated sulfate compounds. On the basis of this compilation, it appears that there is no evidence for an excess enthalpy of mixing for sulfate-H2O systems, except for the first H2O molecule of crystallization. The enthalpy and Gibbs energy of formation of each H2O molecule of crystallization, except the first, in the iron(II) sulfate - H2O system is -295.15 and -238.0 kJ?mol-1, respectively. The absence of an excess enthalpy of mixing is used as the basis for estimating thermodynamic values for a variety of ferrous, ferric, and mixed-valence sulfate salts of relevance to acid-mine drainage systems.

  4. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    Science.gov (United States)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  5. Aerosol Formation during the Combustion of Straw with Addition of Sorbents

    DEFF Research Database (Denmark)

    Zeuthen, Frederik Jacob; Jensen, Peter Arendt; Jensen, Jørgen P.

    2007-01-01

    , calcium phosphate, Bentonite, ICA5000, and clay. The addition of chalk increased the aerosol mass concentration by 24%. Experiments in a laminar flow aerosol condenser with the six sorbents were carried out in the laboratory using a synthetic flue gas to avoid fluctuations in the alkali feeding......The influence of six sorbents on aerosol formation during the combustion of straw in a 100 MW boiler on a Danish power plant has been studied in full-scale. The following sorbents were studied: ammonium sulfate, monocalcium phosphate, Bentonite, ICA5000, clay, and chalk. Bentonite and ICA5000...... are mixtures of clay minerals and consist mainly of the oxides from Fe, Al, and Si. The straw used was Danish wheat and seed grass. Measurements were also made with increased flow of primary air. The experiments showed between 46% and 70% reduction in particle mass concentrations when adding ammonium sulfate...

  6. 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...

  7. 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.

  8. Long-term competition between sulfate reducing and methanogenic bacteria in UASB reactors treating volatile fatty acids.

    Science.gov (United States)

    Omil, F; Lens, P; Visser, A; Hulshoff Pol, L W; Lettinga, G

    1998-03-20

    The competition between acetate utilizing methane-producing bacteria (MB) and sulfate-reducing bacteria (SRB) was studied in mesophilic (30 degrees C) upflow anaerobic sludge bed (UASB) reactors (upward velocity 1 m h-1; pH 8) treating volatile fatty acids and sulfate. The UASB reactors treated a VFA mixture (with an acetate:propionate:butyrate ratio of 5:3:2 on COD basis) or acetate as the sole substrate at different COD:sulfate ratios. The outcome of the competition was evaluated in terms of conversion rates and specific methanogenic and sulfidogenic activities. The COD:sulfate ratio was a key factor in the partitioning of acetate utilization between MB and SRB. In excess of sulfate (COD:sulfate ratio lower than 0.67), SRB became predominant over MB after prolonged reactor operation: 250 and 400 days were required to increase the amount of acetate used by SRB from 50 to 90% in the reactor treating, respectively, the VFA mixture or acetate as the sole substrate. The competition for acetate was further studied by dynamic simulations using a mathematical model based on the Monod kinetic parameters of acetate utilizing SRB and MB. The simulations confirmed the long term nature of the competition between these acetotrophs. A high reactor pH (+/-8), a short solid retention time (acetate-utilising SRB to outcompete MB. Copyright 1998 John Wiley & Sons, Inc.

  9. Sulfate adsorption on goethite

    Energy Technology Data Exchange (ETDEWEB)

    Rietra, R P.J.J.; Hiemstra, T; Riemsdijk, W.H. van

    1999-10-15

    Recent spectroscopic work has suggested that only one surface species of sulfate is dominant on hematite. Sulfate is therefore a very suitable anion to test and develop adsorption models for variable charge minerals. The authors have studied sulfate adsorption on goethite covering a large range of sulfate concentrations, surface coverages, pH values, and electrolyte concentrations. Four different techniques were used to cover the entire range of conditions. For characterization at low sulfate concentrations, below the detection limit of sulfate with ICP-AES, the authors used proton-sulfate titrations at constant pH. Adsorption isotherms were studied for the intermediate sulfate concentration range. Acid-base titrations in sodium sulfate and electromobility were used for high sulfate concentrations. All the data can be modeled with one adsorbed species if it is assumed that the charge of adsorbed sulfate is spatially distributed in the interface. The charge distribution of sulfate follows directly from modeling the proton-sulfate adsorption stoichoimemtry sine this stoichiometry is independent of the intrinsic affinity constant of sulfate. The charge distribution can be related to the structure of the surface complex by use of the Pauling bond valence concept and is in accordance with the microscopic structure found by spectroscopy. The intrinsic affinity constant follows from the other measurements. Modeling of the proton-ion stoichoimetry with the commonly used 2-pK models, where adsorbed ions are treated as point charges, is possible only if at least two surface species for sulfate are used.

  10. Supported zirconium sulfate on carbon nanotubes as water-tolerant solid acid catalyst

    International Nuclear Information System (INIS)

    Juan, Joon Ching; Jiang Yajie; Meng Xiujuan; Cao Weiliang; Yarmo, Mohd Ambar; Zhang Jingchang

    2007-01-01

    A new solid acid of zirconium sulfate (CZ) was successfully supported on carbon nanotube (CNT) for esterification reaction. Preparation conditions of the supported CZ have been investigated, to obtain highest catalytic activity for esterification reaction. XRD, TEM, BET, X-ray photoelectron spectra (XPS) and in situ FTIR analysis has also been carried out to understand the characteristics of the catalyst. In the esterification of acrylic acid with n-octanol, the supported CZ exhibited high catalytic activity and stability. The catalytic activity was nearly unchanged during four times of reuse. XRD and TEM analysis indicated that CZ was finely dispersed on CNT. XPS analysis shows that the CZ species was preserved and the chemical environment of the CZ has changed after loaded on CNT. This finding show that CNT as CZ support is an efficient water-tolerant solid acid

  11. Reaction pathway of the degradation of the p-hydroxybenzoic acid by sulfate radical generated by ionizing radiations

    International Nuclear Information System (INIS)

    Criquet, Justine; Leitner, Nathalie Karpel Vel

    2015-01-01

    The degradation of p-hydroxybenzoic acid (HBA) in aqueous solutions by ionizing radiation was studied. The phenolic pollutant was easily removed by the electron beam irradiation, as more than 80% of the initial 100 µM introduced was degraded for a dose of 600 Gy. It was shown that the addition of persulfate, producing the sulfate radical as additional reactive species, induced a change in the reaction pathway. LC–MS analyses were performed in order to identify the different by-products formed. In the absence of persulfate, the main by-product formed was 3,4-dihydroxybenzoic acid, while in presence of persulfate, 1,4-benzoquinone was detected and the hydroxylated by-products were not present. A reaction pathway of HBA degradation by hydroxyl and sulfate radicals was proposed from the identification of the chemical structure of the different by-products detected. The influences of pH and dissolved oxygen were also studied. A high decline of HBA degradation was observed at pH 11 compared to pH 4.5, this decrease was minimized in the presence of persulfate. The dissolved oxygen concentration was found to be a limiting parameter of HBA degradation, however an excess of dissolved oxygen in solution did not improve the degradation to a large extent. - Highlights: • p-Hydroxybenzoic acid (HBA) is easily removed by e-beam irradiation. • The sulfate radicals formed from persulfate induce loss of the benzoic acid skeleton. • The dissolved oxygen concentration is a limiting parameter of the HBA degradation. • The effect of pH is minimized in presence of persulfate

  12. Size distributions of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

    Science.gov (United States)

    Mkoma, S. L.; Kawamura, K.

    2012-09-01

    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 reactions on aerosols under strong solar

  13. 21 CFR 184.1443 - Magnesium sulfate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium sulfate. 184.1443 Section 184.1443 Food... Specific Substances Affirmed as GRAS § 184.1443 Magnesium sulfate. (a) Magnesium sulfate (MgSO4·7H2O, CAS... magnesium oxide, hydroxide, or carbonate with sulfuric acid and evaporating the solution to crystallization...

  14. Hydrolysis of glyoxal in water-restricted environments: formation of organic aerosol precursors through formic acid catalysis.

    Science.gov (United States)

    Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

    2014-06-12

    The hydrolysis of glyoxal involving one to three water molecules and also in the presence of a water molecule and formic acid has been investigated. Our results show that glyoxal-diol is the major product of the hydrolysis and that formic acid, through its ability to facilitate intermolecular hydrogen atom transfer, is considerably more efficient than water as a catalyst in the hydrolysis process. Additionally, once the glyoxal-diol is formed, the barrier for further hydrolysis to form the glyoxal-tetrol is effectively reduced to zero in the presence of a single water and formic acid molecule. There are two important implications arising from these findings. First, the results suggest that under the catalytic influence of formic acid, glyoxal hydrolysis can impact the growth of atmospheric aerosols. As a result of enhanced hydrogen bonding, mediated through their polar OH functional groups, the diol and tetrol products are expected to have significantly lower vapor pressure than the parent glyoxal molecule; hence they can more readily partition into the particle phase and contribute to the growth of secondary organic aerosols. In addition, our findings provide insight into how glyoxal-diol and glyoxal-tetrol might be formed under atmospheric conditions associated with water-restricted environments and strongly suggest that the formation of these precursors for secondary organic aerosol growth is not likely restricted solely to the bulk aqueous phase as is currently assumed.

  15. Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation.

    Science.gov (United States)

    Claff, Salirian R; Sullivan, Leigh A; Burton, Edward D; Bush, Richard T; Johnston, Scott G

    2011-11-01

    The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. Aerosol composition and source apportionment in Santiago de Chile

    International Nuclear Information System (INIS)

    Artaxo, Paulo; Oyola, Pedro; Martinez, Roberto

    1999-01-01

    Santiago de Chile, Sao Paulo and Mexico City are Latin American urban areas that suffer from heavy air pollution. In order to study air pollution in Santiago area, an aerosol source apportionment study was designed to measure ambient aerosol composition and size distribution for two downtown sampling sites in Santiago. The aerosol monitoring stations were operated in Gotuzo and Las Condes during July and August 1996. The study employed stacked filter units (SFU) for aerosol sampling, collecting fine mode aerosol (dp 10 mass of particles smaller than 10 μm) and black carbon concentration were also measured. Particle-Induced X-ray Emission (PIXE) was used to measure the concentration of 22 trace elements at levels below 0.5 ng m -3 . Quantitative aerosol source apportionment was performed using Absolute Principal Factor Analysis (APFA). Very high aerosol concentrations were observed (up to 400 μg/m 3 PM 10 ). The main aerosol particle sources in Santiago are resuspended soil dust and traffic emissions. Coarse particles account for 63% of PM 10 aerosol in Gotuzo and 53% in Las Condes. A major part of this component is resuspended soil dust. In the fine fraction, resuspended soil dust accounts for 15% of fine mass, and the aerosols associated with transportation activities account for a high 64% of the fine particle mass. Sulfate particle is an important component of the aerosol in Santiago, mainly originating from gas-to-particle conversion from SO 2 . In the Gotuzo site, sulfates are the highest aerosol component, accounting for 64.5% of fine mass. Direct traffic emissions are generally mixed with resuspended soil dust. It is difficult to separate the two components, because the soil dust in downtown Santiago is contaminated with Pb, Br, Cl, and other heavy metals that are also tracers for traffic emissions. Residual oil combustion is observed, with the presence of V, S and Ni. An aerosol components from industrial emissions is also present, with the presence of

  17. Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

    Science.gov (United States)

    Kawamura, Kimitaka; Barrie, Leonard A.; Toom-Sauntry, Desiree

    2010-12-01

    Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (oxalic acid by GC ranged from 6.5-59.1 ng m -3 (av. 26.0 ng m -3, median 26.2 ng m -3) whereas those by IC ranged from 6.6-52.1 ng m -3 (av. 26.6 ng m -3, median 25.4 ng m -3). They showed a good correlation ( r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.

  18. The influence of different black carbon and sulfate mixing methods on their optical and radiative properties

    International Nuclear Information System (INIS)

    Zhang, Hua; Zhou, Chen; Wang, Zhili; Zhao, Shuyun; Li, Jiangnan

    2015-01-01

    Three different internal mixing methods (Core–Shell, Maxwell-Garnett, and Bruggeman) and one external mixing method are used to study the impact of mixing methods of black carbon (BC) with sulfate aerosol on their optical properties, radiative flux, and heating rate. The optical properties of a mixture of BC and sulfate aerosol particles are considered for three typical bands. The results show that mixing methods, the volume ratio of BC to sulfate, and relative humidity have a strong influence on the optical properties of mixed aerosols. Compared to internal mixing, external mixing underestimates the particle mass absorption coefficient by 20–70% and the particle mass scattering coefficient by up to 50%, whereas it overestimates the particle single scattering albedo by 20–50% in most cases. However, the asymmetry parameter is strongly sensitive to the equivalent particle radius, but is only weakly sensitive to the different mixing methods. Of the internal methods, there is less than 2% difference in all optical properties between the Maxwell-Garnett and Bruggeman methods in all bands; however, the differences between the Core–Shell and Maxwell-Garnett/Bruggeman methods are usually larger than 15% in the ultraviolet and visible bands. A sensitivity test is conducted with the Beijing Climate Center Radiation transfer model (BCC-RAD) using a simulated BC concentration that is typical of east-central China and a sulfate volume ratio of 75%. The results show that the internal mixing methods could reduce the radiative flux more effectively because they produce a higher absorption. The annual mean instantaneous radiative force due to BC–sulfate aerosol is about –3.18 W/m 2 for the external method and –6.91 W/m 2 for the internal methods at the surface, and –3.03/–1.56/–1.85 W/m 2 for the external/Core–Shell/(Maxwell-Garnett/Bruggeman) methods, respectively, at the tropopause. - Highlights: • The aerosol optical properties with different mixing

  19. Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry

    Science.gov (United States)

    Ding, W.; Hsu, C.

    2008-12-01

    Currently, the investigations on aerosol water-soluble organic compounds (WSOCs) formed by burning biomass have become increasingly concerned with the role of these compounds in atmospheric chemistry and their effect on climate, because they have great potential to influence cloud formation, precipitation, and climate on both global and regional scales. Of these compounds, low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) have attracted the most interest because of their properties as specific tracers for the burning of biomass. In this study, a modified injection-port derivatization and gas chromatography - mass spectrometry method was developed and evaluated for rapid determination of LMW dicarboxylic acids in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) dissolved in methanol used as the ion-pair solution gave excellent yield for di-butyl ester low-molecular weight derivatives. Solid-phase extraction method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 67 to 86% with relative standard deviation (RSD) less than 13%. The concentrations of dicarboxylated C2, C3, C4, C5 and C6-C10 in atmospheric aerosols ranged from 91-240 ng/m3, 11-56 ng/m3, 12-49 ng/m3, 8-35 ng/m3 and n.d. to 17 ng/m3, respectively. Oxalic (C2) acid was the dominant dicarboxylic acids detected in aerosol samples. The total concentrations of the LMW dicarboxylic acids (from C2 to C10) correspond to 2.2 to 2.6% of the total aerosol mass.

  20. The effect of copper sulfate, potassium permanganate, and peracetic acid on Ichthyobodo necator in channel catfish

    Science.gov (United States)

    Ichthyobodo necator is a single celled biflagellate that can cause significant mortalities in fish, particularly young, tank-reared fish. Copper sulfate (CuSO4), potassium permanganate (KMnO4) and peracetic acid (PAA) were evaluated for effectiveness against Ichthybodosis in juvenile channel catfis...

  1. Chinese hamster ovary cell mutants defective in heparan sulfate biosynthesis

    International Nuclear Information System (INIS)

    Bame, K.J.; Kiser, C.S.; Esko, J.D.

    1987-01-01

    The authors have isolated Chinese hamster ovary cell mutants defective in proteoglycan synthesis by radiographic screening for cells unable to incorporate 35 SO 4 into acid-precipitable material. Some mutants did not incorporate 35 SO 4 into acid-precipitable material, whereas others incorporated about 3-fold less radioactivity. HPLC anion exchange chromatographic analysis of radiolabelled glycosaminoglycans isolated from these mutants revealed many are defective in heparan sulfate biosynthesis. Mutants 803 and 677 do not synthesize heparan sulfate, although they produce chondroitin sulfate: strain 803 makes chondroitin sulfate normally, whereas 677 overaccumulates chondroitin sulfate by a factor of three. These mutants fall into the same complementation group, suggesting that the mutations are allelic. A second group of heparan sulfate biosynthetic mutants, consisting of cell lines 625, 668 and 679, produce undersulfated heparan sulfate and normal chondroitin sulfate. Treatment of the chains with nitrous acid should determine the position of the sulfate groups along the chain. These mutants may define a complementation group that is defective in the enzymes which modify the heparan sulfate chain. To increase the authors repertoire of heparan sulfate mutants, they are presently developing an in situ enzyme assay to screen colonies replica plated on filter discs for sulfotransferase defects

  2. Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

    Directory of Open Access Journals (Sweden)

    L. Marelle

    2017-10-01

    Full Text Available In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols (1 a correction to the sedimentation of aerosols, (2 dimethyl sulfide (DMS oceanic emissions and gas-phase chemistry, (3 an improved representation of the dry deposition of trace gases over seasonal snow, and (4 an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5 correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6 couple and further test the recent KF-CuP (Kain–Fritsch + Cumulus Potential cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC, sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone, the improved surface temperatures over sea ice (surface ozone, BC, and sulfate, and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone. DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

  3. Corrosion Inhibition of Mild Steel in Hydrochloric Acid by Sodium Lauryl Sulfate (SLS)

    OpenAIRE

    Atul Kumar

    2008-01-01

    Effect of Sodium Lauryl Sulfate (SLS), a surfactant on corrosion of mild steel in 1 M hydrochloric acid was studied using three techniques namely: weight loss, electrochemical polarization and metallurgical research microscopy. Results obtained reveal that SLS is good inhibitor and shows very good corrosion inhibition efficiency (IE). The IE was found to vary with concentration of inhibitor and temperature. The electrochemical polarization result revealed that SLS is anodic in nature.

  4. Calorimetric investigation of solution heat of rare earth sulfates in acid solutions

    International Nuclear Information System (INIS)

    Vasin, S.K.; Babkin, A.G.; Kessler, Yu.M.

    1978-01-01

    To determine the thermodynamic characteristics of sulfates of rare elements an adiabatic airtight calorimeter has been developed, enabling measurement of minor heat effects of processes in aggressive media with an absolute error of about 5x10 -3 cal, the temperature sensitivity being no less than 2x10 -5 C 0 . The calorimeter is schematically represented. Measured with the aid of the calorimeter was the heat of dissolution of TiOSO 4 x2H 2 O in chloric acid solutions

  5. Removal of Arsenic Using Acid/Metal-Tolerant Sulfate Reducing Bacteria: A New Approach for Bioremediation of High-Arsenic Acid Mine Waters

    Directory of Open Access Journals (Sweden)

    Jennyfer Serrano

    2017-12-01

    Full Text Available Fluvial sediments, soils, and natural waters in northern Chile are characterized by high arsenic (As content. Mining operations in this area are potential sources of As and other metal contaminants, due to acid mine drainage (AMD generation. Sulfate Reducing Bacteria (SRB has been used for the treatment of AMD, as they allow for the reduction of sulfate, the generation of alkalinity, and the removal of dissolved heavy metals and metalloids by precipitation as insoluble metal sulfides. Thus, SRB could be used to remove As and other heavy metals from AMD, however the tolerance of SRB to high metal concentrations and low pH is limited. The present study aimed to quantify the impact of SRB in As removal under acidic and As-Fe-rich conditions. Our results show that SRB tolerate low pH (up to 3.5 and high concentrations of As (~3.6 mg·L−1. Batch experiments showed As removal of up to 73%, Iron (Fe removal higher than 78% and a neutralization of pH from acidic to circum-neutral conditions (pH 6–8. In addition, XRD analysis showed the dominance of amorphous minerals, while Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM-EDX analysis showed associations between As, Fe, and sulfur, indicating the presence of Fe-S-As compounds or interaction of As species with amorphous and/or nanocrystalline phases by sorption processes. These results indicate that the As removal was mediated by acid/metal-tolerant SRB and open the potential for the application of new strains of acid/metal-tolerant SRB for the remediation of high-As acid mine waters.

  6. Linking remotely sensed aerosol types to their chemical composition

    Science.gov (United States)

    Dawson, K. W.; Kacenelenbogen, M. S.; Johnson, M. S.; Burton, S. P.; Hostetler, C. A.; Meskhidze, N.

    2016-12-01

    Aerosol types measured during the Ship-Aircraft Bio-Optical Research (SABOR) experiment are related to GEOS-Chem model chemical composition. The application for this procedure to link model chemical components to aerosol type is desirable for understanding aerosol evolution over time. The Mahalanobis distance (DM) statistic is used to cluster model groupings of five chemical components (organic carbon, black carbon, sea salt, dust and sulfate) in a way analogous to the methods used by Burton et al. [2012] and Russell et al. [2014]. First, model-to-measurement evaluation is performed by collocating vertically resolved aerosol extinction from SABOR High Spectral Resolution LiDAR (HSRL) to the GEOS-Chem nested high-resolution data. Comparisons of modeled-to-measured aerosol extinction are shown to be within 35% ± 14%. Second, the model chemical components are calculation into five variables to calculate the DM and cluster means and covariances for each HSRL-retrieved aerosol type. The layer variables from the model are aerosol optical depth (AOD) ratios of (i) sea salt and (ii) dust to total AOD, mass ratios of (iii) total carbon (i.e. sum of organic and black carbon) to the sum of total carbon and sulfate (iv) organic carbon to black carbon, and (v) the natural log of the aerosol-to-molecular extinction ratio. Third, the layer variables and at most five out of twenty SABOR flights are used to form the pre-specified clusters for calculating DM and to assign an aerosol type. After determining the pre-specified clusters, model aerosol types are produced for the entire vertically resolved GEOS-Chem nested domain over the United States and the model chemical component distributions relating to each type are recorded. Resulting aerosol types are Dust/Dusty Mix, Maritime, Smoke, Urban and Fresh Smoke (separated into `dark' and `light' by a threshold of the organic to black carbon ratio). Model-calculated DM not belonging to a specific type (i.e. not meeting a threshold

  7. Aerosol ionic components at Mt. Heng in central southern China: abundances, size distribution, and impacts of long-range transport.

    Science.gov (United States)

    Gao, Xiaomei; Xue, Likun; Wang, Xinfeng; Wang, Tao; Yuan, Chao; Gao, Rui; Zhou, Yang; Nie, Wei; Zhang, Qingzhu; Wang, Wenxing

    2012-09-01

    Water-soluble ions in PM(2.5) were continuously measured, along with the measurements of many other species and collection of size-resolved aerosol samples, at the summit of Mt. Heng in the spring of 2009, to understand the sources of aerosols in rural central southern China. The mean concentrations of SO(4)(2-), NH(4)(+) and NO(3)(-) in PM(2.5) were 8.02, 2.94 and 1.47 μg/m(3), indicating a moderate aerosol pollution level at Mt. Heng. Water-soluble ions composed approximately 40% of the PM(2.5) mass on average. PM(2.5) was weakly acidic with about 66% of the samples being acidic. SO(4)(2-), NO(3)(-) and NH(4)(+) exhibited similar diurnal patterns with a broad afternoon maximum. SO(4)(2-) and NH(4)(+) were mainly present in the fine aerosols with a peak in the droplet mode of 0.56-1 μm, suggesting the important role of cloud processing in the formation of aerosol sulfate. NO(3)(-) was largely distributed in the coarse particles with a predominant peak in the size-bin of 3.2-5.6 μm. Long-distance transport of processed air masses, dust aerosols, and cloud/fog processes were the major factors determining the variations of fine aerosol at Mt. Heng. The results at Mt. Heng were compared with those obtained from our previous study at Mt. Tai in north China. The comparison revealed large differences in the aerosol characteristics and processes between southern and northern China. Backward trajectories indicated extensive transport of anthropogenic pollution from the coastal regions of eastern/northern China and the Pearl River Delta (PRD) to Mt. Heng in spring, highlighting the need for regionally coordinated control measures for the secondary pollutants. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Aerosol chemistry and the effect of aerosol water content on visibility impairment and radiative forcing in Guangzhou during the 2006 Pearl River Delta campaign.

    Science.gov (United States)

    Jung, Jinsang; Lee, Hanlim; Kim, Young J; Liu, Xingang; Zhang, Yuanhang; Gu, Jianwei; Fan, Shaojia

    2009-08-01

    Optical and chemical aerosol measurements were obtained from 2 to 31 July 2006 at an urban site in the metropolitan area of Guangzhou (China) as part of the Program of Regional Integrated Experiment of Air Quality over Pearl River Delta (PRIDE-PRD2006) to investigate aerosol chemistry and the effect of aerosol water content on visibility impairment and radiative forcing. During the PRIDE-PRD2006 campaign, the average contributions of ammonium sulfate, organic mass by carbon (OMC), elemental carbon (EC), and sea salt (SS) to total PM(2.5) mass were measured to be 36.5%, 5.7%, 27.1%, 7.8%, and 3.7%, respectively. Compared with the clean marine period, (NH(4))(2)SO(4), NH(4)NO(3), and OMC were all greatly enhanced (by up to 430%) during local haze periods via the accumulation of a secondary aerosol component. The OMC dominance increased when high levels of biomass burning influenced the measurement site while (NH(4))(2)SO(4) and OMC did when both biomass burning and industrial emissions influenced it. The effect of aerosol water content on the total light-extinction coefficient was estimated to be 34.2%, of which 25.8% was due to aerosol water in (NH(4))(2)SO(4), 5.1% that in NH(4)NO(3), and 3.3% that in SS. The average mass-scattering efficiency (MSE) of PM(10) particles was determined to be 2.2+/-0.6 and 4.6+/-1.7m(2)g(-1) under dry (RHwater content, but MSE and SSA are also highly sensitive. It can be concluded that sulfate and carbonaceous aerosol, as well as aerosol water content, play important roles in the processes that determine visibility impairment and radiative forcing in the ambient atmosphere of the Guangzhou urban area.

  9. Use of copper sulfate and peracetic acid as therapeutants on fish: can these replace formalin?

    Science.gov (United States)

    Copper sulfate (CuSO4) and peracetic acid (PAA) are compounds that have been found to be useful in several areas of aquaculture around the world. In the United States, CuSO4 is used for treatment of an ectoparasite (Ichthyophthirius multifiliis) on fish (Straus 1993; Tieman and Goodwin 2001), and s...

  10. Role of dissimilatory sulfate reduction in wetlands constructed for acid coal mine drainage (AMD) treatment. Master's thesis

    International Nuclear Information System (INIS)

    Taddeo, F.J.

    1991-01-01

    Five constructed wetlands with different organic substrates were exposed to the same quantity/quality of acid mine drainage (AMD). During the 16-month exposure to AMD, all wetlands accumulated S in the forms of organic and reduced inorganic S and Fe in the form of iron sulfides. Iron sulfide and probably most of the organic S(C-bonded S) accumulation were end products of bacterial dissimilatory sulfate reduction. Results of study support the notion that sulfate reduction and accumulation of Fe sulfides contribute to Fe retention in wetlands exposed to AMD. Detailed information is provided

  11. In situ acidity and pH of size-fractionated aerosols during a recent smoke-haze episode in Southeast Asia.

    Science.gov (United States)

    Behera, Sailesh N; Cheng, Jinping; Balasubramanian, Rajasekhar

    2015-10-01

    The characterization of aerosol acidity has received increased attention in recent years due to its influence on atmospheric visibility, climate change and human health. Distribution of water soluble inorganic (WSI) ions in 12 different size fractions of aerosols was investigated under two different atmospheric conditions (smoke-haze and non-haze periods) in 2012 using the Micro-Orifice Uniform Deposit Impactor (MOUDI) and nano-MOUDI for the first time in Singapore. To estimate the in situ acidity ([H(+)]Ins) and in situ aerosol pH (pHIS), the Aerosol Inorganic Model version-IV under deliquescent mode of airborne particles was used at prevailing ambient temperature and relative humidity. The study revealed an increase in the levels of airborne particulate matter (PM) mass and concentrations of WSI ions for all size fractions during the smoke-haze period, which was caused by the trans-boundary transport of biomass burning-impacted air masses from Indonesia. A bimodal distribution was observed for concentrations of SO4(2-), NO3(-), Cl(-), K(+) and Na(+), whereas concentrations of NH4(+), Ca(2+) and Mg(2+) showed a single mode distribution. The concentration of WSI ions in PM1.8 during the smoke-haze period increased by 3.8 (for SO4(2-)) to 10.5 (for K(+)) times more than those observed during the non-haze period. The pHIS were observed to be lower during the smoke-haze period than that during the non-haze period for all size fractions of PM, indicating that atmospheric aerosols were more acidic due to the influence of biomass burning emissions. The particles in the accumulation mode were more acidic than those in the coarse mode.

  12. Increases to Biogenic Secondary Organic Aerosols from SO2 and NOx in the Southeastern US

    Science.gov (United States)

    Russell, L. M.; Liu, J.; Ruggeri, G.; Takahama, S.; Claflin, M. S.; Ziemann, P. J.; Lee, A.; Murphy, B.; Pye, H. O. T.; Ng, N. L.; McKinney, K. A.; Surratt, J. D.

    2017-12-01

    During the 2013 Southern Oxidant and Aerosol Study, Fourier Transform Infrared Spectroscopy (FTIR) and Aerosol Mass Spectrometer (AMS) measurements of submicron mass were collected at Look Rock, Tennessee, and Centreville, Alabama. The low NOx, low wind, little rain, and increased daytime isoprene emissions led to multi-day stagnation events at Look Rock that provided clear evidence of particle-phase sulfate enhancing biogenic secondary organic aerosol (bSOA) by selective uptake. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% bSOA, with the latter including "sulfate-related bSOA" that correlated to sulfate (r=0.72) and "nitrate-related bSOA" that correlated to nitrate (r=0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r>0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity=0.97) and the time series correlation (r=0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants. Since Look Rock had much less NOx than Centreville, comparing the bSOA at the two sites provides an evaluation of the role of NOx for bSOA. CO and submicron sulfate and OM concentrations were 15-60 % higher at Centreville than at Look Rock but their time series had moderate correlations of r= 0.51, 0.54, and 0.47, respectively. However, NOx had no correlation (r=0.08) between the two sites. OM correlated with the higher NOx levels at Centreville but with O3 at Look Rock. OM sources identified by Positive Matrix Factorization had three very similar factors at both sites from FTIR

  13. Easy Volcanic Aerosol (EVA v1.0: an idealized forcing generator for climate simulations

    Directory of Open Access Journals (Sweden)

    M. Toohey

    2016-11-01

    Full Text Available Stratospheric sulfate aerosols from volcanic eruptions have a significant impact on the Earth's climate. To include the effects of volcanic eruptions in climate model simulations, the Easy Volcanic Aerosol (EVA forcing generator provides stratospheric aerosol optical properties as a function of time, latitude, height, and wavelength for a given input list of volcanic eruption attributes. EVA is based on a parameterized three-box model of stratospheric transport and simple scaling relationships used to derive mid-visible (550 nm aerosol optical depth and aerosol effective radius from stratospheric sulfate mass. Precalculated look-up tables computed from Mie theory are used to produce wavelength-dependent aerosol extinction, single scattering albedo, and scattering asymmetry factor values. The structural form of EVA and the tuning of its parameters are chosen to produce best agreement with the satellite-based reconstruction of stratospheric aerosol properties following the 1991 Pinatubo eruption, and with prior millennial-timescale forcing reconstructions, including the 1815 eruption of Tambora. EVA can be used to produce volcanic forcing for climate models which is based on recent observations and physical understanding but internally self-consistent over any timescale of choice. In addition, EVA is constructed so as to allow for easy modification of different aspects of aerosol properties, in order to be used in model experiments to help advance understanding of what aspects of the volcanic aerosol are important for the climate system.

  14. Corrosion Inhibition of Mild Steel in Hydrochloric Acid by Sodium Lauryl Sulfate (SLS

    Directory of Open Access Journals (Sweden)

    Atul Kumar

    2008-01-01

    Full Text Available Effect of Sodium Lauryl Sulfate (SLS, a surfactant on corrosion of mild steel in 1 M hydrochloric acid was studied using three techniques namely: weight loss, electrochemical polarization and metallurgical research microscopy. Results obtained reveal that SLS is good inhibitor and shows very good corrosion inhibition efficiency (IE. The IE was found to vary with concentration of inhibitor and temperature. The electrochemical polarization result revealed that SLS is anodic in nature.

  15. Stratospheric Aerosol Measurements

    Science.gov (United States)

    Pueschel, Rudolf, F.; Gore, Warren J. (Technical Monitor)

    1998-01-01

    Stratospheric aerosols affect the atmospheric energy balance by scattering and absorbing solar and terrestrial radiation. They also can alter stratospheric chemical cycles by catalyzing heterogeneous reactions which markedly perturb odd nitrogen, chlorine and ozone levels. Aerosol measurements by satellites began in NASA in 1975 with the Stratospheric Aerosol Measurement (SAM) program, to be followed by the Stratospheric Aerosol and Gas Experiment (SAGE) starting in 1979. Both programs employ the solar occultation, or Earth limb extinction, techniques. Major results of these activities include the discovery of polar stratospheric clouds (PSCs) in both hemispheres in winter, illustrations of the impacts of major (El Chichon 1982 and Pinatubo 1991) eruptions, and detection of a negative global trend in lower stratospheric/upper tropospheric aerosol extinction. This latter result can be considered a triumph of successful worldwide sulfur emission controls. The SAGE record will be continued and improved by SAGE III, currently scheduled for multiple launches beginning in 2000 as part of the Earth Observing System (EOS). The satellite program has been supplemented by in situ measurements aboard the ER-2 (20 km ceiling) since 1974, and from the DC-8 (13 km ceiling) aircraft beginning in 1989. Collection by wire impactors and subsequent electron microscopic and X-ray energy-dispersive analyses, and optical particle spectrometry have been the principle techniques. Major findings are: (1) The stratospheric background aerosol consists of dilute sulfuric acid droplets of around 0.1 micrometer modal diameter at concentration of tens to hundreds of monograms per cubic meter; (2) Soot from aircraft amounts to a fraction of one percent of the background total aerosol; (3) Volcanic eruptions perturb the sulfuric acid, but not the soot, aerosol abundance by several orders of magnitude; (4) PSCs contain nitric acid at temperatures below 195K, supporting chemical hypotheses

  16. Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

    Directory of Open Access Journals (Sweden)

    M. S. Shalamzari

    2016-06-01

    Full Text Available We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC precursors for polar organosulfates with molecular weights (MWs 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles (GLVs 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack, and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfooxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α,β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013. The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl

  17. Reactions and mass spectra of complex particles using Aerosol CIMS

    Science.gov (United States)

    Hearn, John D.; Smith, Geoffrey D.

    2006-12-01

    Aerosol chemical ionization mass spectrometry (CIMS) is used both on- and off-line for the analysis of complex laboratory-generated and ambient particles. One of the primary advantages of Aerosol CIMS is the low degree of ion fragmentation, making this technique well suited for investigating the reactivity of complex particles. To demonstrate the usefulness of this "soft" ionization, particles generated from meat cooking were reacted with ozone and the composition was monitored as a function of reaction time. Two distinct kinetic regimes were observed with most of the oleic acid in these particles reacting quickly but with 30% appearing to be trapped in the complex mixture. Additionally, detection limits are measured to be sufficiently low (100-200 ng/m3) to detect some of the more abundant constituents in ambient particles, including sulfate, which is measured in real-time at 1.2 [mu]g/m3. To better characterize complex aerosols from a variety of sources, a novel off-line collection method was also developed in which non-volatile and semi-volatile organics are desorbed from particles and concentrated in a cold U-tube. Desorption from the U-tube followed by analysis with Aerosol CIMS revealed significant amounts of nicotine in cigarette smoke and levoglucosan in oak and pine smoke, suggesting that this may be a useful technique for monitoring particle tracer species. Additionally, secondary organic aerosol formed from the reaction of ozone with R-limonene and volatile organics from orange peel were analyzed off-line showing large molecular weight products (m/z > 300 amu) that may indicate the formation of oligomers. Finally, mass spectra of ambient aerosol collected offline reveal a complex mixture of what appears to be highly processed organics, some of which may contain nitrogen.

  18. Kinetics and Mechanistic Chemistry of Oxidation of Butacaine Sulfate by Chloramine-B in Acid Medium

    International Nuclear Information System (INIS)

    Shubha, Jayachamarajapura Pranesh; Kotabagi, Vinutha; Puttaswamy

    2012-01-01

    Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in HClO 4 medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both [CAB] o , and [substrate] o , and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced

  19. Characterization of a chondroitin sulfate hydrogel for nerve root regeneration

    Science.gov (United States)

    Conovaloff, Aaron; Panitch, Alyssa

    2011-10-01

    Brachial plexus injury is a serious medical problem that affects many patients annually, with most cases involving damage to the nerve roots. Therefore, a chondroitin sulfate hydrogel was designed to both serve as a scaffold for regenerating root neurons and deliver neurotrophic signals. Capillary electrophoresis showed that chondroitin sulfate has a dissociation constant in the micromolar range with several common neurotrophins, and this was determined to be approximately tenfold stronger than with heparin. It was also revealed that nerve growth factor exhibits a slightly stronger affinity for hyaluronic acid than for chondroitin sulfate. However, E8 chick dorsal root ganglia cultured in the presence of nerve growth factor revealed that ganglia cultured in chondroitin sulfate scaffolds showed more robust growth than those cultured in control gels of hyaluronic acid. It is hypothesized that, despite the stronger affinity of nerve growth factor for hyaluronic acid, chondroitin sulfate serves as a better scaffold for neurite outgrowth, possibly due to inhibition of growth by hyaluronic acid chains.

  20. Rural continental aerosol properties and processes observed during the Hohenpeissenberg Aerosol Characterization Experiment (HAZE2002

    Directory of Open Access Journals (Sweden)

    N. Hock

    2008-02-01

    Full Text Available Detailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD in Southern Germany.

    Online measurements included: Size-resolved chemical composition of submicron particles; total particle number concentrations and size distributions over the diameter range of 3 nm to 9 μm; gas-phase concentration of monoterpenes, CO, O3, OH, and H2SO4. Filter sampling and offline analytical techniques were used to determine: Fine particle mass (PM2.5, organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5, and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins.

    Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 μg m−3, arithmetic mean and standard deviation accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 μg m−3. The relative proportions of non-refractory submicron particle components were: (23±39% ammonium nitrate, (27±23% ammonium sulfate, and (50±40% organics (OM1. OM1 was closely correlated with PM1 (r2=0.9 indicating a near-constant ratio of non-refractory organics and inorganics.

    The average ratio of OM1 to OC2.5 was 2.1±1.4, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA over hydrocarbon-like organic aerosol (HOA inferred from the AMS results (4:1, and also with the high abundance of proteins (~3% indicating a high proportion of primary biological material (~30% in PM2.5. This finding was confirmed by low abundance of PAHs (<1 ng m−3 and EC (<1 μg m−3 in PM2.5 and detection of several

  1. Intercontinental Transport of Aerosols: Implication for Regional Air Quality

    Science.gov (United States)

    Chin, Mian; Diehl, Thomas; Ginoux, Paul

    2006-01-01

    Aerosol particles, also known as PM2.5 (particle diameter less than 2.5 microns) and PM10 (particle diameter less than 10 microns), is one of the key atmospheric components that determine ambient air quality. Current US air quality standards for PM10 (particles with diameter air pollution problems, aerosols can be transported on a hemispheric or global scale. In this study, we use the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model to quantify contributions of long-range transport vs. local/regional pollution sources and from natural vs. anthropogenic sources to PM concentrations different regions. In particular, we estimate the hemispheric impact of anthropogenic sulfate aerosols and dust from major source areas on other regions in the world. The GOCART model results are compared with satellite remote sensing and ground-based network measurements of aerosol optical depth and concentrations.

  2. 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.

  3. A case study of the highly time-resolved evolution of aerosol chemical and optical properties in urban Shanghai, China

    Directory of Open Access Journals (Sweden)

    Y. Huang

    2013-04-01

    Full Text Available Characteristics of the chemical and optical properties of aerosols in urban Shanghai and their relationship were studied over a three-day period in October 2011. A suite of real-time instruments, including an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS, a Monitor for AeRosols and GAses (MARGA, a Cavity Ring Down Spectrometer (CRDS, a nephelometer and a Scanning Mobility Particle Sizer (SMPS, was employed to follow the quick changes of the aerosol properties within the 72 h sampling period. The origin of the air mass arriving in Shanghai during this period shifted from the East China Sea to the northwest area of China, offering a unique opportunity to observe the evolution of aerosols influenced by regional transport from the most polluted areas in China. According to the meteorological conditions and temporal characterizations of the chemical and optical properties, the sampling period was divided into three periods. During Period 1 (00:00–23:00 LT, 13 October, the aerosols in urban Shanghai were mainly fresh and the single scattering albedo varied negatively with the emission of elemental carbon, indicating that local sources dominated. Period 2 (23:00 LT on 13 October to 10:00 LT on 15 October was impacted by regionally transported pollutants and had the highest particulate matter (PM mass loading and the lowest particle acidity, characterized by large fractions of aged particles and high secondary ion (nitrate, sulfate and ammonium mass concentrations. Comparison between ATOFMS particle acidity and quantitative particle acidity by MARGA indicated the significance of semi-quantitative calculation in ATOFMS. Two sub-periods were identified in Period 2 based on the scattering efficiency of PM1 mass. Period 3 (from 10:00 LT on 15 October to 00:00 LT on 16 October had a low PM1/PM10 ratio and a new particle formation event. The comparison of these sub-periods highlights the influence of particle mixing state on aerosol optical properties

  4. Bicarbonate sulfate exchange in canalicular rat liver plasma membrane vesicles

    International Nuclear Information System (INIS)

    Meier, P.J.; Valantinas, J.; Hugentobler, G.; Rahm, I.

    1987-01-01

    The mechanism(s) and driving forces for biliary excretion of sulfate were investigated in canalicular rat liver plasma membrane vesicles (cLPM). Incubation of cLPM vesicles in the presence of an inside-to-outside (in, out) bicarbonate gradient but not pH or out-to-in sodium gradients, stimulated sulfate uptake 10-fold compared with the absence of bicarbonate and approximately 2-fold above sulfate equilibrium (overshoot). Initial rates of this bicarbonate gradient-driven [ 35 S]-sulfate uptake were saturable with increasing concentrations of sulfate and could be inhibited by probenecid, N-(4-azido-2-nitrophenyl)-2-aminoethylsulfonate, acetazolamide, furosemide, 4-acetamideo-4'-isothiocyanostilbene-2,2'-disulfonic acid, and 4,4'-diisothiocyanostilbene-2,2'-disulfonic acid (IC 50 , ∼40 μM). Cisinhibition of initial bicarbonate gradient-stimulated sulfate uptake and transstimulation of sulfate uptake in the absence of bicarbonate were observed with sulfate, thiosulfate, and oxalate but not with chloride, nitrate, phosphate, acetate, lactate, glutamate, aspartate, cholate, taurocholate, dehydrocholate, taurodehydrocholate, and reduced or oxidized glutathione. These findings indicate the presence of a sulfate (oxalate)-bicarbonate anion exchange system in canalicular rat liver plasma membranes. These findings support the concept that bicarbonate-sensitive transport system might play an important role in bile acid-independent canalicular bile formation

  5. Chemically-resolved aerosol volatility measurements from two megacity field studies

    Directory of Open Access Journals (Sweden)

    J. A. Huffman

    2009-09-01

    Full Text Available The volatilities of different chemical species in ambient aerosols are important but remain poorly characterized. The coupling of a recently developed rapid temperature-stepping thermodenuder (TD, operated in the range 54–230°C with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS during field studies in two polluted megacities has enabled the first direct characterization of chemically-resolved urban particle volatility. Measurements in Riverside, CA and Mexico City are generally consistent and show ambient nitrate as having the highest volatility of any AMS standard aerosol species while sulfate showed the lowest volatility. Total organic aerosol (OA showed volatility intermediate between nitrate and sulfate, with an evaporation rate of 0.6%·K−1 near ambient temperature, although OA dominates the residual species at the highest temperatures. Different types of OA were characterized with marker ions, diurnal cycles, and positive matrix factorization (PMF and show significant differences in volatility. Reduced hydrocarbon-like OA (HOA, a surrogate for primary OA, POA, oxygenated OA (OOA, a surrogate for secondary OA, SOA, and biomass-burning OA (BBOA separated with PMF were all determined to be semi-volatile. The most aged OOA-1 and its dominant ion, CO2+, consistently exhibited the lowest volatility, with HOA, BBOA, and associated ions for each among the highest. The similar or higher volatility of HOA/POA compared to OOA/SOA contradicts the current representations of OA volatility in most atmospheric models and has important implications for aerosol growth and lifetime. A new technique using the AMS background signal was demonstrated to quantify the fraction of species up to four orders-of-magnitude less volatile than those detectable in the MS mode, which for OA represent ~5% of the non-refractory (NR OA signal. Our results strongly imply that all OA types should be considered

  6. Composition and sources of winter and summertime aerosols at Ny Alesund, Spitsbergen

    International Nuclear Information System (INIS)

    Maenhaut, W.; Cornille, P.; Pacyna, J.M.

    1991-01-01

    Filter samples of < 2.5 μm aerosol were collected in (late) winter of 1983, 1984, 1986, and 1987 and in the summer of 1984, 1986, and 1987 at Ny Alesund, Spitsbergen, and analyzed for over 40 elements by a combination of INAA and PIXE. The data sets of the various sampling campaigns and the combined winter and combined summer data were examined by receptor modeling, including absolute principal component analysis (APCA), chemical mass balance (CMB) and multiple linear regression (MLR) techniques. APCA yielded four components, both for the winter and for the summer aerosol. For the winter aerosol, the components were identified as a general pollution component, crustal dust, sea-salt, and a halogen (Br,I) component. The CMB and MLR calculations were used to obtain source (source region) apportionments for the anthropogenic trace elements and for sulfate. For the summer, about 50% of the sulfate was attributed to a marine biogenic source

  7. Characterization of aerosol over the Northern South China Sea during two cruises in 2003

    Science.gov (United States)

    Zhang, Xingying; Zhuang, Guoshun; Guo, Jinghua; Yin, Kedong; Zhang, Peng

    Atmospheric transport of trace elements has been found to be an important pathway for their input to the ocean. TSP, PM10, and PM2.5 aerosol samples were collected over the Northern South China Sea in two cruises in 2003 to estimate the input of aerosol from continent to the ocean. About 23 elements and 14 soluble ions in aerosol samples were measured. The average mass concentration of TSP in Cruise I in January (78 μg m -3) was ˜twice of that in Cruise II in April (37 μg m -3). Together with the crustal component, heavy metals from pollution sources over the land (especially from the industry and automobiles in Guangzhou) were transported to and deposited into the ocean. The atmospheric MSA concentrations in PM2.5 (0.048 μg m -3 in Cruise I and 0.043 μg m -3 in Cruise II) over Northern South China Sea were comparable to those over other coastal regions. The ratio of non-sea-salt (NSS)-sulfate to MSA is 103-655 for Cruise I and 15-440 for Cruise II in PM2.5 samples, which were much higher than those over remote oceans. The estimated anthropogenic sulfate accounts for 83-98% in Cruise I and 63-95% in Cruise II of the total NSS-sulfate. Fe (II) concentration in the aerosols collected over the ocean ranged from 0.1 to 0.9 μg m -3, accounting for 16-82% of the total iron in the aerosol, which could affect the marine biogeochemical cycle greatly.

  8. Biologically-induced precipitation of sphalerite-wurtzite nanoparticles by sulfate-reducing bacteria: implications for acid mine drainage treatment.

    Science.gov (United States)

    Castillo, Julio; Pérez-López, Rafael; Caraballo, Manuel A; Nieto, José M; Martins, Mónica; Costa, M Clara; Olías, Manuel; Cerón, Juan C; Tucoulou, Rémi

    2012-04-15

    Several experiments were conducted to evaluate zinc-tolerance of sulfate-reducing bacteria (SRB) obtained from three environmental samples, two inocula from sulfide-mining districts and another inoculum from a wastewater treatment plant. The populations of SRB resisted zinc concentrations of 260 mg/L for 42 days in a sulfate-rich medium. During the experiments, sulfate was reduced to sulfide and concentrations in solution decreased. Zinc concentrations also decreased from 260 mg/L to values below detection limit. Both decreases were consistent with the precipitation of newly-formed sphalerite and wurtzite, two polymorphs of ZnS, forming <2.5-μm-diameter spherical aggregates identified by microscopy and synchrotron-μ-XRD. Sulfate and zinc are present in high concentrations in acid mine drainage (AMD) even after passive treatments based on limestone dissolution. The implementation of a SRB-based zinc removal step in these systems could completely reduce the mobility of all metals, which would improve the quality of stream sediments, water and soils in AMD-affected landscapes. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland

    Science.gov (United States)

    Richard, A.; Gianini, M. F. D.; Mohr, C.; Furger, M.; Bukowiecki, N.; Minguillón, M. C.; Lienemann, P.; Flechsig, U.; Appel, K.; Decarlo, P. F.; Heringa, M. F.; Chirico, R.; Baltensperger, U.; Prévôt, A. S. H.

    2011-09-01

    Time and size resolved data of trace elements were obtained from measurements with a rotating drum impactor (RDI) and subsequent X-ray fluorescence spectrometry. Trace elements can act as indicators for the identification of sources of particulate matter Switzerland. Eight different sources were identified for the three examined size ranges (PM1-0.1, PM2.5-1 and PM10-2.5): secondary sulfate, wood combustion, fire works, road traffic, mineral dust, de-icing salt, industrial and local anthropogenic activities. The major component was secondary sulfate for the smallest size range; the road traffic factor was found in all three size ranges. This trace element analysis is complemented with data from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS), assessing the PM1 fraction of organic aerosols. A separate PMF analysis revealed three factors related to three of the sources found with the RDI: oxygenated organic aerosol (OOA, related to inorganic secondary sulfate), hydrocarbon-like organic aerosol (HOA, related to road traffic) and biomass burning organic aerosol (BBOA), explaining 60 %, 22 % and 17 % of total measured organics, respectively. Since different compounds are used for the source classification, a higher percentage of the ambient PM10 mass concentration can be apportioned to sources by the combination of both methods.

  10. Direct Measurement of pH in Individual Particles via Raman Microspectroscopy and Variation in Acidity with Relative Humidity.

    Science.gov (United States)

    Rindelaub, Joel D; Craig, Rebecca L; Nandy, Lucy; Bondy, Amy L; Dutcher, Cari S; Shepson, Paul B; Ault, Andrew P

    2016-02-18

    Atmospheric aerosol acidity is an important characteristic of aqueous particles, which has been linked to the formation of secondary organic aerosol by catalyzing reactions of oxidized organic compounds that have partitioned to the particle phase. However, aerosol acidity is difficult to measure and traditionally estimated using indirect methods or assumptions based on composition. Ongoing disagreements between experiments and thermodynamic models of particle acidity necessitate improved fundamental understanding of pH and ion behavior in high ionic strength atmospheric particles. Herein, Raman microspectroscopy was used to determine the pH of individual particles (H2SO4+MgSO4) based on sulfate and bisulfate concentrations determined from νs(SO4(2-)) and νs(HSO4(-)), the acid dissociation constant, and activity coefficients from extended Debye-Hückel calculations. Shifts in pH and peak positions of νs(SO4(2-)) and νs(HSO4(-)) were observed as a function of relative humidity. These results indicate the potential for direct spectroscopic determination of pH in individual particles and the need to improve fundamental understanding of ion behavior in atmospheric particles.

  11. Source apportionment of submicron organic aerosol collected from Atlanta, Georgia, during 2014-2015 using the aerosol chemical speciation monitor (ACSM)

    Science.gov (United States)

    Rattanavaraha, Weruka; Canagaratna, Manjula R.; Budisulistiorini, Sri Hapsari; Croteau, Philip L.; Baumann, Karsten; Canonaco, Francesco; Prevot, Andre S. H.; Edgerton, Eric S.; Zhang, Zhenfa; Jayne, John T.; Worsnop, Douglas R.; Gold, Avram; Shaw, Stephanie L.; Surratt, Jason D.

    2017-10-01

    , which supports that BBOA is likely derived from fresh biomass/residential burning. However, weaker correlation with levoglucosan (R = 0.38) in summer suggested a more aged aerosol. During warmer seasons, OA from the reactive uptake of isoprene epoxydiols (IEPOX) onto acidic sulfate aerosol was resolved by ME-2 (denoted as IEPOX-OA), averaging 25-29% of the total OA mass. Temporal variation of IEPOX-OA was nearly coincident with that of 91Fac OA (a factor dominated by a distinct ion at m/z 91). The largest contribution of IEPOX-OA to total OA (29%) was found in summer, whereas the largest contribution of 91Fac to total OA (24%) occurred in early fall. Moderate negative correlation between IEPOX-OA and aerosol acidity was observed during late spring (-0.67) and summer (-0.42), consistent with laboratory studies showing that IEPOX-OA is enhanced in the presence of acidic aerosols. Finally, the largest OA mass in all seasons (46-70% of total OA) was derived from oxygenated OA denoted as low-volatility oxygenated OA (LV-OOA) and semi-volatile oxygenated OA (SV-OOA).

  12. The effect of aspirated barium sulfate, iodixanol, and diatrizoic acid on survival and lung injury in a lagomorph model.

    Science.gov (United States)

    Siddiqui, M Tausif; Litts, Juliana K; Cheney, Diane M; Kuhn, Maggie A; Nativ-Zeltzer, Nogah; Belafsky, Peter C

    2017-05-01

    Contrast agents are an integral component of the video fluoroscopic swallow study. Agents commonly used include barium sulfate (E-Z Paque), iodixanol (Visipaque), and diatrizoic acid (Gastrografin). Barium is water insoluble, whereas iodixanol and diatrizoic acid are water-soluble iodine-based agents. The detrimental effect of these agents on the lungs has not been systematically evaluated. Our aim was to evaluate and compare the effects of aspirated barium, iodixanol, and diatrizoic acid on pulmonary injury in a lagomorph model. Animal model. Twenty adult male New Zealand White rabbits were divided into four groups (n = 5). Group 1 received 3 mL of barium sulfate injected into the trachea for 3 consecutive days. Group 2 received 3 mL of iodixanol injected into the trachea for 3 consecutive days. Group 3 received 3 mL of diatrizoic acid injected into the trachea for 3 consecutive days. A control group received 3 mL of air injected into the trachea under an identical protocol. All animals were euthanized on day 4, and the lung and trachea were harvested for blinded histopathologic analysis. The primary outcome measure was survival. The secondary endpoint was a blinded, histologic grading system of lung injury. Two animals in the barium group, one in the diatrizoic acid group, and 0 animals in the iodixanol and control groups died. The overall lung injury score for the barium (60.60 ± 6.34) and iodixanol groups (52.30 ± 3.11) were significantly higher (worse) than the diatrizoic acid (49.60 ± 7.64) and control groups (37.80 ± 3.56) (P barium sulfate (E-Z Paque) over 3 consecutive days causes more severe lung injury in a lagomorph model than 3 mL of aspirated iodixanol (Visipaque) and diatrizoic acid (Gastrografin). Diatrizoic acid caused the least histologic evidence of lung injury. NA Laryngoscope, 127:E148-E152, 2017. © 2017 The American Laryngological, Rhinological and Otological Society, Inc.

  13. Dissolution of sulfate scales

    Energy Technology Data Exchange (ETDEWEB)

    Hen, J.

    1991-11-26

    This patent describes a composition for the removal of sulfate scale from surfaces. It comprises: an aqueous solution of about 0.1 to 1.0 molar concentration of an aminopolycarboxylic acid (APCA) containing 1 to 4 amino groups or a salt thereof, and about 0.1 to 1.0 molar concentration of a second component which is diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) or a salt thereof, or aminotri (methylenephosphonic acid) (ATMP) or a salt thereof as an internal phase enveloped by a hydrocarbon membrane phase which is itself emulsified in an external aqueous phase, the hydrocarbon membrane phase continuing a complexing agent weaker for the cations of the sulfate scale than the APCA and DTPMP or ATMP, any complexing agent for the cations in the external aqueous phase being weaker than that in the hydrocarbon membrane phase.

  14. In vitro tests for aerosol deposition. III: effect of inhaler insertion angle on aerosol deposition.

    Science.gov (United States)

    Delvadia, Renish R; Longest, P Worth; Hindle, Michael; Byron, Peter R

    2013-06-01

    Inhaler orientation with respect to a patient's mouth may be an important variable determining the efficiency of aerosol lung delivery. The effect of insertion angle on regional deposition was evaluated for a series of inhalers using concurrent in vitro and computational fluid dynamics (CFD) analysis. Geometrically realistic physical mouth-throat (MT) and upper tracheobronchial (TB) models were constructed to connect different inhalers at a series of insertion angles relative to the horizontal plane of the model. These models were used to assess albuterol sulfate deposition from the Novolizer(®) dry powder inhaler (DPI), Proventil(®) HFA pressurized metered dose inhaler (MDI), and Respimat(®) Soft Mist™ Inhaler (SMI) following the actuation of a single dose. Drug deposition from Novolizer DPI was studied for Salbulin(®) and an experimental "drug only" formulation. Albuterol sulfate was recovered and quantified from the device and the MT and TB regions. Significant differences in MT and total lung dose (TLD) of albuterol sulfate deposition were not observed for Salbulin Novolizer DPI and Respimat SMI inserted at different angles. In contrast, drug-only Novolizer DPI and Proventil HFA MDI showed a significant difference in MT and TLD deposition using different insertion angles. For drug-only Novolizer DPI and Proventil HFA MDI, the lowest and the highest MT depositions were observed at +10° and -20°, respectively; for Respimat SMI and Salbulin Novolizer DPI, these angles were -10° and +10°, and +20° and -20°, respectively. CFD simulations were in agreement with the experimental results and illustrated shifts in local particle deposition associated with changes in insertion angle. The effect of inhaler orientation at the inhaler-mouth interface on MT aerosol deposition appeared to be dependent on velocity, aerosol size, and formulation. These findings not only demonstrate the need for patient education on correct inhaler orientation, but provide important

  15. Influence of Atmospheric Processes on the Solubility and Composition of Iron in Saharan Dust.

    Science.gov (United States)

    Longo, Amelia F; Feng, Yan; Lai, Barry; Landing, William M; Shelley, Rachel U; Nenes, Athanasios; Mihalopoulos, Nikolaos; Violaki, Kalliopi; Ingall, Ellery D

    2016-07-05

    Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation state became more reduced, and aerosol acidity increased. Atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.

  16. On the contribution of organics to the North East Atlantic aerosol number concentration

    International Nuclear Information System (INIS)

    Bialek, Jakub; Dall’Osto, Manuel; Monahan, Ciaran; O’Dowd, Colin; Beddows, David

    2012-01-01

    k-means statistical-cluster analysis of submicron aerosol size distributions is combined with coincident humidity tandem differential mobility analyser data, leading to five unique aerosol categories for hygroscopic growth factors (HGFs): low sea-salt background marine, high sea-salt background marine, coastal nucleation, open ocean nucleation and anthropogenically influenced scenarios. When considering only marine conditions, and generic aerosol species associated with this environment (e.g. non-sea-salt sulfate, sea-salt, partly soluble organic matter and water insoluble organic matter), the two-year annual average contribution to aerosol number concentration from the different generic species was made up as follows: 46% (30–54%) of partially modified ammonium sulfate particles; 23% (11–40%) of partially modified sea-salt; and the remaining 31% (25–35%) contribution attributed to two distinct organic species as evidenced by different, but low, HGFs. The analysis reveals that on annual timescales, ∼30% of the submicron marine aerosol number concentration is sourced from predominantly organic aerosol while 60% of the anthropogenic aerosol number is predominantly organic. Coastal nucleation events show the highest contribution of the lowest HGF mode (1.19), although this contribution is more likely to be influenced by inorganic iodine oxides. While organic mass internally mixed with inorganic salts will lower the activation potential of these mixed aerosol types, thereby potentially reducing the concentration of cloud condensation nuclei (CCN), pure organic water soluble particles are still likely to be activated into cloud droplets, thereby increasing the concentration of CCN. A combination of dynamics and aerosol concentrations will determine which effect will prevail under given conditions. (letter)

  17. Water content of aged aerosol

    OpenAIRE

    G. J. Engelhart; L. Hildebrandt; E. Kostenidou; N. Mihalopoulos; N. M. Donahue; S. N. Pandis

    2010-01-01

    The composition and physical properties of aged atmospheric aerosol were characterized at a remote sampling site on the northern coast of Crete, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-2008). A reduced Dry-Ambient Aerosol Size Spectrometer (DAASS) was deployed to measure the aerosol water content and volumetric growth factor of fine particulate matter. The particles remained wet even at relative humidity (RH) as low as 20%. The aerosol was acidic during mo...

  18. The single scattering properties of the aerosol particles as aggregated spheres

    International Nuclear Information System (INIS)

    Wu, Y.; Gu, X.; Cheng, T.; Xie, D.; Yu, T.; Chen, H.; Guo, J.

    2012-01-01

    The light scattering and absorption properties of anthropogenic aerosol particles such as soot aggregates are complicated in the temporal and spatial distribution, which introduce uncertainty of radiative forcing on global climate change. In order to study the single scattering properties of anthorpogenic aerosol particles, the structures of these aerosols such as soot paticles and soot-containing mixtures with the sulfate or organic matter, are simulated using the parallel diffusion limited aggregation algorithm (DLA) based on the transmission electron microscope images (TEM). Then, the single scattering properties of randomly oriented aerosols, such as scattering matrix, single scattering albedo (SSA), and asymmetry parameter (AP), are computed using the superposition T-matrix method. The comparisons of the single scattering properties of these specific types of clusters with different morphological and chemical factors such as fractal parameters, aspect ratio, monomer radius, mixture mode and refractive index, indicate that these different impact factors can respectively generate the significant influences on the single scattering properties of these aerosols. The results show that aspect ratio of circumscribed shape has relatively small effect on single scattering properties, for both differences of SSA and AP are less than 0.1. However, mixture modes of soot clusters with larger sulfate particles have remarkably important effects on the scattering and absorption properties of aggregated spheres, and SSA of those soot-containing mixtures are increased in proportion to the ratio of larger weakly absorbing attachments. Therefore, these complex aerosols come from man made pollution cannot be neglected in the aerosol retrievals. The study of the single scattering properties on these kinds of aggregated spheres is important and helpful in remote sensing observations and atmospheric radiation balance computations.

  19. Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

    Science.gov (United States)

    Sauerwein, Meike; Keung Chan, Chak

    2017-05-01

    Heterogeneous uptake is one of the major mechanisms governing the amounts of short-chain alkylamines and ammonia (NH3) in atmospheric particles. Molar ratios of aminium to ammonium ions detected in ambient aerosols often exceed typical gas phase ratios. The present study investigated the simultaneous uptake of dimethylamine (DMA) and NH3 into sulfuric and oxalic acid particles at gaseous DMA / NH3 molar ratios of 0.1 and 0.5 at 10, 50 and 70 % relative humidity (RH). Single-gas uptake and co-uptake were conducted under identical conditions and compared. Results show that the particulate dimethyl-aminium/ammonium molar ratios (DMAH / NH4) changed substantially during the uptake process, which was severely influenced by the extent of neutralisation and the particle phase state. In general, DMA uptake and NH3 uptake into concentrated H2SO4 droplets were initially similarly efficient, yielding DMAH / NH4 ratios that were similar to DMA / NH3 ratios. As the co-uptake continued, the DMAH / NH4 gradually dropped due to a preferential uptake of NH3 into partially neutralised acidic droplets. At 50 % RH, once the sulfate droplets were neutralised, the stronger base DMA displaced some of the ammonium absorbed earlier, leading to DMAH / NH4 ratios up to four times higher than the corresponding gas phase ratios. However, at 10 % RH, crystallisation of partially neutralised sulfate particles prevented further DMA uptake, while NH3 uptake continued and displaced DMAH+, forming almost pure ammonium sulfate. Displacement of DMAH+ by NH3 has also been observed in neutralised, solid oxalate particles. The results can explain why DMAH / NH4 ratios in ambient liquid aerosols can be larger than DMA / NH3, despite an excess of NH3 in the gas phase. An uptake of DMA to aerosols consisting of crystalline ammonium salts, however, is unlikely, even at comparable DMA and NH3 gas phase concentrations.

  20. Hydration of the sulfuric acid-methylamine complex and implications for aerosol formation.

    Science.gov (United States)

    Bustos, Danielle J; Temelso, Berhane; Shields, George C

    2014-09-04

    The binary H2SO4-H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0-6. Because it is a strong acid-base system, H2SO4-NH2CH3 quickly forms a tightly bound HSO4(-)-NH3CH3(+) complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4-NH2CH3 is -21.8 kcal mol(-1) compared with -16.8 kcal mol(-1) for H2SO4-NH3 and -12.8 kcal mol(-1) for H2SO4-H2O. Adding one to two water molecules to the H2SO4-NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4-NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

  1. Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

    OpenAIRE

    Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić Trošić, Jasna; Gvozdenović, Milica M.

    2012-01-01

    The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipit...

  2. Effect of Zinc Sulfate and Ascorbic Acid on some Morpho-Physiological Traits of Echinacea purpurea (Purple coneflower under Water Deficit Conditions

    Directory of Open Access Journals (Sweden)

    F Farahvash

    2015-05-01

    Full Text Available To quantify the response of some morpho-physiological traits of Echinacea purpurea to thr application of zinc sulfate and ascorbic acid under water deficit, an experiment was carried out in split plot factorial based on RCBD with three replications at the Agricultural Research Station of Islamic Azad University, Tabriz Branch in 2011-12. Experimental factors consisted of water stress as the main factor with three levels (irrigation after70mm evaporation, irrigation after120mm evaporation and irrigation after 170mm evaporation from class A pan, Secondary factor consisted of: application of microelement with two levels (control and application of zinc sulfate 0.005 concentration and ascorbic acid with four levels (not application, application of 50 mg/l of ascorbic acid, application of 100 mg/l of ascorbic acid and application of 150 mg/l of ascorbic acid. The results showed that the effect of water deficit on purple coneflower caused significant differences in diameter of stem, number of flowering branch, stomata density, zinc concentration of aerial parts plant, fresh weight, relative water content of leaf, LAI, proline concentration, crop growth rate, relative growth rate and net assimilation rate. Comparison of means for water deficits between the different levels of drought stress showed that the maximum LAI, with 2.85, belonged to control. Comparison of means for interaction effects between drought stress and application of zinc sulfate revealed that the maximum proline concentration belonged to spraying plants with zinc sulfate at irrigation after 170mm evaporation from class A pan with 10.16 mg/g.fw. Minimum proline concentration was due to without applying zinc sulfate in complete irrigation (control with 0.08 mg/g.fw. Maximum crop growth rate with 6.77 g/m2.day was was related to control and the minimum, with 4.16 g/m2.day, to irrigation after 170mm. Maximum relative crop growth rate, with 0.19 g/m2.day, belonged to control and the

  3. Potential climatic effects of anthropogenic aerosols

    International Nuclear Information System (INIS)

    Pueschel, R.F.

    1993-01-01

    Aerosols act as part of the climate system through their influence on solar and terrestrial radiation. The effect of anthropogenic aerosols on the reduction of visibility is explored in this chapter. Elemental carbon has been identified as the most effective visibility-reducing species. Most of the visibility reduction is due to particles with diameter smaller than 2.5 μm. Studies indicate that sulfate is also a very important aerosol species that results in low visibility and high turbidity. Radiative properties such as aerosol single-scattering albedo values and absorption-to-backscatter ratios purported to produce warming or cooling effects of aerosols are discussed. It is concluded that aerosol clouds have a tendency to cool when they are over a low-albedo surface and have a tendency to warm when they are over high-albedo surfaces such as snow. Anthropogenic aerosols have a tendency to warm the earth's atmospheric system, based on calculations and assumed aerosol optical properties. However, this effect is somewhat offset by the absorption and re-emission into space of infrared terrestrial radiation. The net effect depends on the ratio of the absorption coefficients in the visible and infrared and also on the surface albedo. The effects on infrared radiation are documented for two anthropogenic aerosol sources in the United States, the Denver metropolitan area and power plant plumes in New Mexico, through calculations and measurements. Measured cooling rates within an aerosol plume are not sufficient to offset the warming rate due to absorption of short-wave radiation. Research indicates that anthropogenic aerosols can possibly cause local-scale warming of the atmosphere, but global-scale climatic effects remain an open question

  4. The global impact of the transport sectors on atmospheric aerosol in 2030 – Part 1: Land transport and shipping

    Directory of Open Access Journals (Sweden)

    M. Righi

    2015-01-01

    Full Text Available Using the EMAC (ECHAM/MESSy Atmospheric Chemistry global climate-chemistry model coupled to the aerosol module MADE (Modal Aerosol Dynamics model for Europe, adapted for global applications, we simulate the impact of land transport and shipping emissions on global atmospheric aerosol and climate in 2030. Future emissions of short-lived gas and aerosol species follow the four Representative Concentration Pathways (RCPs designed in support of the Fifth Assessment Report of the Intergovernmental Panel on Climate Change. We compare the resulting 2030 land-transport- and shipping-induced aerosol concentrations to the ones obtained for the year 2000 in a previous study with the same model configuration. The simulations suggest that black carbon and aerosol nitrate are the most relevant pollutants from land transport in 2000 and 2030 and their impacts are characterized by very strong regional variations during this time period. Europe and North America experience a decrease in the land-transport-induced particle pollution, although in these regions this sector remains a major source of surface-level pollution in 2030 under all RCPs. In Southeast Asia, however, a significant increase is simulated, but in this region the surface-level pollution is still controlled by other sources than land transport. Shipping-induced air pollution is mostly due to aerosol sulfate and nitrate, which show opposite trends towards 2030. Sulfate is strongly reduced as a consequence of sulfur reduction policies in ship fuels in force since 2010, while nitrate tends to increase due to the excess of ammonia following the reduction in ammonium sulfate. The aerosol-induced climate impact of both sectors is dominated by aerosol-cloud effects and is projected to decrease between 2000 and 2030, nevertheless still contributing a significant radiative forcing to Earth's radiation budget.

  5. Importance of Sulfate Aerosol in Evaluating the Relative Contributions of Regional Emissions to the Historical Global Temperature Change

    International Nuclear Information System (INIS)

    Andronova, N.; Schlesinger, M.

    2004-01-01

    During the negotiations of the Kyoto Protocol the delegation of Brazil presented an approach for distributing the burden of emissions reductions among the Parties based on the effect of their cumulative historical emissions on the global-average near-surface temperature. The Letter to the Parties does not limit the emissions to be considered to be only greenhouse gas (GHG) emissions. Thus, in this paper we explore the importance of anthropogenic SOx emissions that are converted to sulfate aerosol in the atmosphere, together with the cumulative greenhouse gas emissions, in attributing historical temperature change. We use historical emissions and our simple climate model to estimate the relative contributions to global warming of the regional emissions by four Parties: OECD90, Africa and Latin America, Asia, and Eastern Europe and the Former Soviet Union. Our results show that for most Parties the large warming contributed by their GHG emissions is largely offset by the correspondingly large cooling by their SOx emissions. Thus, OECD90 has become the dominant contributor to recent global warming following its large reduction in SOx emissions after 1980

  6. A study of reactions of sulfur dioxide in the gaseous phase. Production and evolution of aerosols resulting from these reactions

    International Nuclear Information System (INIS)

    Boulaud, Denis

    1977-01-01

    The reactions of sulfur dioxide in the gaseous phase with atmospheric pollutants (NO x ; hydrocarbons) were studied. Experiments showed that NO 2 contribution was significant and suggested that SO 2 transformation into sulfuric acid and sulfates might occur through oxidising agents mainly hydroxyl (OH) and hydro-peroxyl (HO 2 ) radicals. The production and evolution of the resulting aerosols was also studied. It was demonstrated that the effect of water vapour on particle production was significant and that primary embryos were formed from the hetero-molecular homogeneous nucleation acting on water vapour and very likely on sulfuric acid. There was a semi-quantitative agreement between our experimental results and some theoretical investigations on nucleation rate of the system (H 2 O - H 2 SO 4 ). The subsequent growth of particles was studied in a simulation chamber. Finally a model of sulfuric acid vapour evolution in presence of atmospheric aerosols made it possible to extend the previous results as far as possible to the case of atmosphere and then to compare the importance of homogeneous and heterogeneous nucleation of the vapours according to atmospheric conditions. (author) [fr

  7. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

    Directory of Open Access Journals (Sweden)

    W. Rattanavaraha

    2016-04-01

    Full Text Available In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA that contributes to fine particulate matter (PM2.5. Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2, oxides of nitrogen (NOx, and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM, ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS. Sample extracts were analyzed by gas chromatography–electron ionization-mass spectrometry (GC/EI-MS with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM ( ∼  7 to  ∼  20 %. Isoprene-derived SOA tracers correlated with sulfate (SO42− (r2 = 0.34, n = 117 but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML-derived SOA tracers with nitrate radical production (P[NO3] (r2 = 0.57, n = 40 were observed during nighttime, suggesting a

  8. Substantial Seasonal Contribution of Observed Biogenic Sulfate Particles to Cloud Condensation Nuclei.

    Science.gov (United States)

    Sanchez, Kevin J; Chen, Chia-Li; Russell, Lynn M; Betha, Raghu; Liu, Jun; Price, Derek J; Massoli, Paola; Ziemba, Luke D; Crosbie, Ewan C; Moore, Richard H; Müller, Markus; Schiller, Sven A; Wisthaler, Armin; Lee, Alex K Y; Quinn, Patricia K; Bates, Timothy S; Porter, Jack; Bell, Thomas G; Saltzman, Eric S; Vaillancourt, Robert D; Behrenfeld, Mike J

    2018-02-19

    Biogenic sources contribute to cloud condensation nuclei (CCN) in the clean marine atmosphere, but few measurements exist to constrain climate model simulations of their importance. The chemical composition of individual atmospheric aerosol particles showed two types of sulfate-containing particles in clean marine air masses in addition to mass-based Estimated Salt particles. Both types of sulfate particles lack combustion tracers and correlate, for some conditions, to atmospheric or seawater dimethyl sulfide (DMS) concentrations, which means their source was largely biogenic. The first type is identified as New Sulfate because their large sulfate mass fraction (63% sulfate) and association with entrainment conditions means they could have formed by nucleation in the free troposphere. The second type is Added Sulfate particles (38% sulfate), because they are preexisting particles onto which additional sulfate condensed. New Sulfate particles accounted for 31% (7 cm -3 ) and 33% (36 cm -3 ) CCN at 0.1% supersaturation in late-autumn and late-spring, respectively, whereas sea spray provided 55% (13 cm -3 ) in late-autumn but only 4% (4 cm -3 ) in late-spring. Our results show a clear seasonal difference in the marine CCN budget, which illustrates how important phytoplankton-produced DMS emissions are for CCN in the North Atlantic.

  9. 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.

  10. Dispersion Process and Effect of Oleic Acid on Properties of Cellulose Sulfate- Oleic Acid Composite Film

    Science.gov (United States)

    Chen, Guo; Zhang, Bin; Zhao, Jun

    2015-01-01

    The cellulose sulfate (CS) is a newly developed cellulose derivative. The work aimed to investigate the effect of oleic acid (OA) content on properties of CS-OA film. The process of oleic acid dispersion into film was described to evaluate its effect on the properties of the film. Among the formulations evaluated, the OA addition decreased the solubility and water vapor permeability of the CS-OA film. The surface contact angle changed from 64.2° to 94.0° by increasing CS/OA ratio from 1:0 to 1:0.25 (w/w). The TS increased with OA content below 15% and decreased with OA over 15%, but the ε decreased with higher OA content. The micro-cracking matrices and micro pores in the film indicated the condense structure of the film destroyed by the incorporation of oleic acid. No chemical interaction between the OA and CS was observed in the XRD and FTIR spectrum. Film formulation containing 2% (w/w) CS, 0.3% (w/w) glycerol and 0.3% (w/w) OA, showed good properties of mechanic, barrier to moisture and homogeneity.

  11. Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

    Science.gov (United States)

    Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

    2016-05-01

    In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

  12. Particle-Resolved Modeling of Aerosol Mixing State in an Evolving Ship Plume

    Science.gov (United States)

    Riemer, N. S.; Tian, J.; Pfaffenberger, L.; Schlager, H.; Petzold, A.

    2011-12-01

    The aerosol mixing state is important since it impacts the particles' optical and CCN properties and thereby their climate impact. It evolves continuously during the particles' residence time in the atmosphere as a result of coagulation with other particles and condensation of secondary aerosol species. This evolution is challenging to represent in traditional aerosol models since they require the representation of a multi-dimensional particle distribution. While modal or sectional aerosol representations cannot practically resolve the aerosol mixing state for more than a few species, particle-resolved models store the composition of many individual aerosol particles directly. They thus sample the high-dimensional composition state space very efficiently and so can deal with tens of species, fully resolving the mixing state. Here we use the capabilities of the particle-resolved model PartMC-MOSAIC to simulate the evolution of particulate matter emitted from marine diesel engines and compare the results to aircraft measurements made in the English Channel in 2007 as part of the European campaign QUANTIFY. The model was initialized with values of gas concentrations and particle size distributions and compositions representing fresh ship emissions. These values were obtained from a test rig study in the European project HERCULES in 2006 using a serial four-stroke marine diesel engine operating on high-sulfur heavy fuel oil. The freshly emitted particles consisted of sulfate, black carbon, organic carbon and ash. We then tracked the particle population for several hours as it evolved undergoing coagulation, dilution with the background air, and chemical transformations in the aerosol and gas phase. This simulation was used to compute the evolution of CCN properties and optical properties of the plume on a per-particle basis. We compared our results to size-resolved data of aged ship plumes from the QUANTIFY Study in 2007 and showed that the model was able to reproduce

  13. Sulfur deposition changes under sulfate geoengineering conditions: quasi-biennial oscillation effects on the transport and lifetime of stratospheric aerosols

    Science.gov (United States)

    Visioni, Daniele; Pitari, Giovanni; Tuccella, Paolo; Curci, Gabriele

    2018-02-01

    Sustained injection of sulfur dioxide (SO2) in the tropical lower stratosphere has been proposed as a climate engineering technique for the coming decades. Among several possible environmental side effects, the increase in sulfur deposition deserves additional investigation. In this study we present results from a composition-climate coupled model (University of L'Aquila Composition-Chemistry Model, ULAQ-CCM) and a chemistry-transport model (Goddard Earth Observing System Chemistry-Transport Model, GEOS-Chem), assuming a sustained lower-stratospheric equatorial injection of 8 Tg SO2 yr-1. Total S deposition is found to globally increase by 5.2 % when sulfate geoengineering is deployed, with a clear interhemispheric asymmetry (+3.8 and +10.3 % in the Northern Hemisphere (NH) and the Southern Hemisphere (SH), due to +2.2 and +1.8 Tg S yr-1, respectively). The two models show good consistency, both globally and on a regional scale under background and geoengineering conditions, except for S-deposition changes over Africa and the Arctic. The consistency exists with regard to time-averaged values but also with regard to monthly and interannual deposition changes. The latter is driven essentially by the variability in stratospheric large-scale transport associated with the quasi-biennial oscillation (QBO). Using an externally nudged QBO, it is shown how a zonal wind E shear favors aerosol confinement in the tropical pipe and a significant increase in their effective radius (+13 % with respect to W shear conditions). The net result is an increase in the downward cross-tropopause S flux over the tropics with dominant E shear conditions with respect to W shear periods (+0.61 Tg S yr-1, +42 %, mostly due to enhanced aerosol gravitational settling) and a decrease over the extratropics (-0.86 Tg S yr-1, -35 %, mostly due to decreased large-scale stratosphere-troposphere exchange of geoengineering sulfate). This translates into S-deposition changes that are significantly

  14. Molecular composition of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

    Science.gov (United States)

    Mkoma, S. L.; Kawamura, K.

    2013-02-01

    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 dry season whereas those to water-soluble organic carbon were 2.2% and 4.7% in PM2.5 during wet season and 3.1% and 5.8% in PM10 during dry season. The higher ratios in dry season suggest an enhanced photochemical oxidation of organic precursors probably via heterogeneous reactions on

  15. Thermal stability and surface acidity of mesoporous silica doubly doped by incorporation of sulfate and zirconium ions

    International Nuclear Information System (INIS)

    Salas, P.; Chen, L.F.; Wang, J.A.; Armendariz, H.; Guzman, M.L.; Montoya, J.A.; Acosta, D.R.

    2005-01-01

    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 4 ) 2 SO 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 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 4 2- /(ZrO 2 + SiO 2 ) increased from 0.1 to 0.3 but decreased as it reached 0.5, which is consistent with the results of 29 Si MAS-NMR and XRD analysis. Compared to Si-MCM-41, the (Q 2 + Q 3 )/Q 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

  16. Two-Column Aerosol Project (TCAP) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Berg, Larry K [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-05-01

    This study included the deployment of the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s Mobile Facility (AMF), ARM Mobile Aerosol Observing System (MAOS) and the ARM Aerial Facility (AAF). The study was a collaborative effort involving scientists from DOE national laboratories, NOAA, NASA, and universities. The AAF and MAOS were deployed for two approximately month-long Intensive Operational Periods (IOPs) conducted in June 2012 and February 2013. Seasonal differences in the aerosol chemical and optical properties observed using the AMF, AAF, and MAOS are presented in this report. The total mass loading of aerosol is found to be much greater in the summer than in the winter, with the difference associated with greater amounts of organic aerosol. The mass fraction of organic aerosol is much reduced in the winter, when sulfate is the dominant aerosol type. Surprisingly, very little sea-salt aerosol was observed in the summer. In contrast, much more sea salt aerosol was observed in the winter. The mass loading of black carbon is nearly the same in both seasons. These differences lead to a relative increase in the aerosol light absorption in the winter and an associated decrease in observed single-scattering albedo. Measurements of aerosol mixing state were made using a single-particle mass spectrometer, which showed that the majority of the summertime aerosol consisted of organic compounds mixed with various amounts of sulfate. A number of other findings are also summarized in the report, including: impact of aerosol layers aloft on the column aerosol optical depth; documentation of the aerosol properties at the AMF; differences in the aerosol properties associated with both columns, which are not systematic but reflect the complicated meteorological and chemical processes that impact aerosol as it is advected away from North America; and new instruments and data-processing techniques for measuring both aerosol and

  17. A New WRF-Chem Treatment for Studying Regional Scale Impacts of Cloud-Aerosol Interactions in Parameterized Cumuli

    Energy Technology Data Exchange (ETDEWEB)

    Berg, Larry K.; Shrivastava, ManishKumar B.; Easter, Richard C.; Fast, Jerome D.; Chapman, Elaine G.; Liu, Ying

    2015-01-01

    A new treatment of cloud-aerosol interactions within parameterized shallow and deep convection has been implemented in WRF-Chem that can be used to better understand the aerosol lifecycle over regional to synoptic scales. The modifications to the model to represent cloud-aerosol interactions include treatment of the cloud dropletnumber mixing ratio; key cloud microphysical and macrophysical parameters (including the updraft fractional area, updraft and downdraft mass fluxes, and entrainment) averaged over the population of shallow clouds, or a single deep convective cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. Thesechanges have been implemented in both the WRF-Chem chemistry packages as well as the Kain-Fritsch cumulus parameterization that has been modified to better represent shallow convective clouds. Preliminary testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS) as well as a high-resolution simulation that does not include parameterized convection. The simulation results are used to investigate the impact of cloud-aerosol interactions on the regional scale transport of black carbon (BC), organic aerosol (OA), and sulfate aerosol. Based on the simulations presented here, changes in the column integrated BC can be as large as -50% when cloud-aerosol interactions are considered (due largely to wet removal), or as large as +35% for sulfate in non-precipitating conditions due to the sulfate production in the parameterized clouds. The modifications to WRF-Chem version 3.2.1 are found to account for changes in the cloud drop number concentration (CDNC) and changes in the chemical composition of cloud-drop residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to WRF-Chem version 3.5, and it is anticipated that they

  18. Seasonal latitudinal and secular variations in temperature trend - evidence for influence of anthropogenic sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Hunter, D E; Schwartz, S E; Wagener, R; Benkovitz, C M [University of California at San Diego, La Jolla, CA (United States). Scripps Institute of Oceanography

    1993-11-19

    Tropospheric aerosols increase the shortwave reflectivity of the Earth-atmosphere system both by scattering light directly, in the absence of clouds, and by enhancing cloud reflectivity. The radiative forcing of climate exerted by anthropogenic sulfate aerosols, derived mainly from SO[sub 2] emitted from fossil fuel combustion, is opposite that due to anthropogenic greenhouse gases and is estimated to be of comparable average magnitude in Northern Hemisphere midlatitudes. However, persuasive evidence of climate response to this forcing has thus far been lacking. Here we examine patterns of seasonal and latitudinal variations in temperature anomaly trend for evidence of such a response. Pronounced minima in the rate of temperature increase in summer months in Northern Hemisphere midlatitudes are consistent with the latitudinal distribution of anthropogenic sulfate and changes in the rate of SO[sub 2] emissions over the industrial era.

  19. The smog-fog-smog cycle and acid deposition

    Science.gov (United States)

    Pandis, Spyros N.; Seinfeld, John H.; Pilinis, Christodoulos

    1990-10-01

    A model including descriptions of aerosol and droplet microphysics, gas and aqueous-phase chemistry, and deposition is used to study the transformation of aerosol to fog droplets and back to aerosol in an urban environment. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium and well as in the total aerosol mass concentration. The sulfate produced during fog episodes favors the aerosol particles that have access to most of the fog liquid water which are usually the large particles. Aerosol scavenging efficiencies of around 80 percent are calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition and can introduce errors in the reported values of the ionic species deposition velocities. Differences in the major ionic species deposition velocities can be explained by their distribution over the droplet size spectrum and can be correlated with the species average diameter. Two different expressions are derived for use in fog models for the calculation of the liquid water deposition velocity during fog growth and dissipation stages.

  20. Biochemical and molecular characterization of potential phosphate-solubilizing bacteria in acid sulfate soils and their beneficial effects on rice growth.

    Directory of Open Access Journals (Sweden)

    Qurban Ali Panhwar

    Full Text Available A study was conducted to determine the total microbial population, the occurrence of growth promoting bacteria and their beneficial traits in acid sulfate soils. The mechanisms by which the bacteria enhance rice seedlings grown under high Al and low pH stress were investigated. Soils and rice root samples were randomly collected from four sites in the study area (Kelantan, Malaysia. The topsoil pH and exchangeable Al ranged from 3.3 to 4.7 and 1.24 to 4.25 cmol(c kg(-1, respectively, which are considered unsuitable for rice production. Total bacterial and actinomycetes population in the acidic soils were found to be higher than fungal populations. A total of 21 phosphate-solubilizing bacteria (PSB including 19 N2-fixing strains were isolated from the acid sulfate soil. Using 16S rRNA gene sequence analysis, three potential PSB strains based on their beneficial characteristics were identified (Burkholderia thailandensis, Sphingomonas pituitosa and Burkholderia seminalis. The isolated strains were capable of producing indoleacetic acid (IAA and organic acids that were able to reduce Al availability via a chelation process. These PSB isolates solubilized P (43.65% existing in the growth media within 72 hours of incubation. Seedling of rice variety, MR 219, grown at pH 4, and with different concentrations of Al (0, 50 and 100 µM was inoculated with these PSB strains. Results showed that the bacteria increased the pH with a concomitant reduction in Al concentration, which translated into better rice growth. The improved root volume and seedling dry weight of the inoculated plants indicated the potential of these isolates to be used in a bio-fertilizer formulation for rice cultivation on acid sulfate soils.

  1. Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Wang

    2016-07-01

    Full Text Available In this work, the Aerodyne soot particle – aerosol mass spectrometer (SP-AMS was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD of China, for online characterization of the submicron aerosols (PM1. The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics. The average PM1 concentration was found to be 28.2 µg m−3, with organics (45 % as the most abundant component, following by sulfate (19.3 %, nitrate (13.6 %, ammonium (11.1 %, rBC (9.7 %, and chloride (1.3 %. These PM1 species together can reconstruct ∼ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (< 100 nm vacuum aerodynamic diameter were dominated by organics and rBC, while large particles had significant contributions from secondary inorganic species. Source apportionment of organic aerosols (OA yielded four OA subcomponents, including hydrocarbon-like OA (HOA, cooking-related OA (COA, semi-volatile oxygenated OA (SV-OOA, and low-volatility oxygenated OA (LV-OOA. Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA dominated the total OA mass (55.5 %, but primary organic aerosol (POA, equal to the sum of HOA and COA can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand

  2. Distribution of sulfur aerosol precursors in the SPCZ released by continuous volcanic degassing at Ambrym, Vanuatu

    Science.gov (United States)

    Lefèvre, Jérôme; Menkes, Christophe; Bani, Philipson; Marchesiello, Patrick; Curci, Gabriele; Grell, Georg A.; Frouin, Robert

    2016-08-01

    The Melanesian Volcanic Arc (MVA) emits about 12 kT d- 1 of sulfur dioxide (SO2) to the atmosphere from continuous passive (non-explosive) volcanic degassing, which contributes 20% of the global SO2 emission from volcanoes. Here we assess, from up-to-date and long-term observations, the SO2 emission of the Ambrym volcano, one of the dominant volcanoes in the MVA, and we investigate its role as sulfate precursor on the regional distribution of aerosols, using both satellite observations and model results at 1° × 1° spatial resolution from WRF-Chem/GOCART. Without considering aerosol forcing on clouds, our model parameterizations for convection, vertical mixing and cloud properties provide a reliable chemical weather representation, making possible a cross-examination of model solution and observations. This preliminary work enables the identification of biases and limitations affecting both the model (missing sources) and satellite sensors and algorithms (for aerosol detection and classification) and leads to the implementation of improved transport and aerosol processes in the modeling system. On the one hand, the model confirms a 50% underestimation of SO2 emissions due to satellite swath sampling of the Ozone Monitoring Instrument (OMI), consistent with field studies. The OMI irregular sampling also produces a level of noise that impairs its monitoring capacity during short-term volcanic events. On the other hand, the model reveals a large sensitivity on aerosol composition and Aerosol Optical Depth (AOD) due to choices of both the source function in WRF-Chem and size parameters for sea-salt in FlexAOD, the post-processor used to compute offline the simulated AOD. We then proceed to diagnosing the role of SO2 volcanic emission in the regional aerosol composition. The model shows that both dynamics and cloud properties associated with the South Pacific Convergence Zone (SPCZ) have a large influence on the oxidation of SO2 and on the transport pathways of

  3. The uptake of HO2 radicals to organic aerosols

    Science.gov (United States)

    Matthews, Pascale; Krapf, Manuel; Dommen, Josef; George, Ingrid; Whalley, Lisa; Ingham, Trevor; Baeza-Romero, Maria Teresa; Ammann, Markus; Heard, Dwayne

    2014-05-01

    HOx (OH + HO2) radicals are responsible for the majority of the oxidation in the troposphere and control the concentrations of many trace species in the atmosphere. There have been many field studies where the measured HO2 concentrations have been smaller than the concentration predicted by model calculations [1,2]. The difference has often been attributed to HO2 uptake by aerosols. Organics are a major component of aerosols accounting for 10 - 70 % of their mass [3]. However, there have been very few laboratory studies measuring HO2 uptake onto organic aerosols [4]. Uptake coefficients (γ) were measured for a range of aerosols using a Fluorescence Assay By Gas Expansion (FAGE) detector combined with an aerosol flow tube. HO2 was injected into the flow tube using a moveable injector which allowed first order HO2 decays to be measured along the flow tube both with and without aerosols. Laboratory generated aerosols were made using an atomiser or by homogeneous nucleation. Secondary organic aerosols (SOA) were made using the Paul Scherrer Institute smog chamber and also by means of a Potential Aerosol Mass (PAM) chamber. The total aerosol surface area was then measured using a Scanning Mobility Particle Sizer (SMPS). Experiments were carried out on aerosols containing glutaric acid, glyoxal, malonic acid, stearic acid, oleic acid and squalene. The HO2 uptake coefficients for these species were measured in the range of γ contained elevated levels of transition metal ions. For humic acid the uptake coefficient was highly dependent on humidity and this may be explained by the liquid water content of the aerosols. Measurements were also performed on copper doped aerosols containing different organics. An uptake coefficient of 0.23 ± 0.07 was measured for copper doped ammonium sulphate, however, this was reduced to 0.008 ± 0.009 when EDTA was added in a 1:1 ratio with copper and 0.003 ± 0.004 when oxalic acid was added in a 10:1 ratio with copper. SOA aerosols were

  4. Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system

    Science.gov (United States)

    Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.

    2012-12-01

    Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic

  5. 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.

  6. Applying Limestone or Basalt in Combination with Bio-Fertilizer to Sustain Rice Production on an Acid Sulfate Soil in Malaysia

    Directory of Open Access Journals (Sweden)

    Qurban Ali Panhwar

    2016-07-01

    Full Text Available A study was conducted to determine the efficacy of applying ground magnesium limestone (GML or ground basalt in combination with bio-fertilizer to sustain rice production on an acid sulfate soil in Malaysia. Soils from Kelantan Plains, Malaysia, were treated with GML, ground basalt, bio-fertilizer, GML + bio-fertilizer, and ground basalt + bio-fertilizer (4 t·ha−1 each. Results showed that soil fertility was improved by applying the soil amendments. GML and basalt contain some Zn and Cu; thus, application of these amendments would increase their contents in the soil needed for the healthy growth of rice. Basalt applied in combination with bio-fertilizer appeared to be the best agronomic option to improve the fertility of acid sulfate soils for sustainable rice production in the long run. In addition to increasing Ca, Mg, Zn, and Cu reserves in the soil, water pH increased and precipitated Al3+ and/or Fe2+. Ground basalt is cheaper than GML, but basalt dissolution in the acidic soil was slow. As such, its ameliorative effects could only be seen significantly from the second season onwards. The specially-formulated bio-fertilizer for alleviating the infertility of acid sulfate soil could also enhance rice growth. The use of the bio-fertilizer fortified with N2-fixing bacteria is a green technology that would help reduce NO3− and/or NO2− pollution and reduce the cost of rice production. The phosphate-solubilizing bacteria (PSB present in the bio-fertilizer not only increased the available P, but also helped release organic acids that would inactivate Al3+ and/or Fe2+ via the process of chelation.

  7. Properties of Arctic Aerosol Particles and Residuals of Warm Clouds: Cloud Activation Efficiency and the Aerosol Indirect Effect

    Science.gov (United States)

    Zelenyuk, A.; Imre, D. G.; Leaitch, R.; Ovchinnikov, M.; Liu, P.; Macdonald, A.; Strapp, W.; Ghan, S. J.; Earle, M. E.

    2012-12-01

    Single particle mass spectrometer, SPLAT II, was used to characterize the size, composition, number concentration, density, and shape of individual Arctic spring aerosol. Background particles, particles above and below the cloud, cloud droplet residuals, and interstitial particles were characterized with goal to identify the properties that separate cloud condensation nuclei (CCN) from background aerosol particles. The analysis offers a comparison between warm clouds formed on clean and polluted days, with clean days having maximum particle concentrations (Na) lower than ~250 cm-3, as compared with polluted days, in which maximum concentration was tenfold higher. On clean days, particles were composed of organics, organics mixed with sulfates, biomass burning (BB), sea salt (SS), and few soot and dust particles. On polluted days, BB, organics associated with BB, and their mixtures with sulfate dominated particle compositions. Based on the measured compositions and size distributions of cloud droplet residuals, background aerosols, and interstitial particles, we conclude that these three particle types had virtually the same compositions, which means that cloud activation probabilities were surprisingly nearly composition independent. Moreover, these conclusions hold in cases in which less than 20% or more than 90% of background particles got activated. We concluded that for the warm clouds interrogated in this study particle size played a more important factor on aerosol CCN activity. Comparative analysis of all studied clouds reveals that aerosol activation efficiency strongly depends on the aerosol concentrations, such that at Na <200 cm-3, nearly all particles activate, and at higher concentrations the activation efficiency is lower. For example, when Na was greater than 1500 cm-3, less than ~30% of particles activated. The data suggest that as the number of nucleated droplets increases, condensation on existing droplets effectively competes with particle

  8. Formation of sulphite, cysteic acid and taurine from sulphate by the egg embryo; Formation de sulfite, d'acide cysteique et de taurine a partir de sulfate par l'oeuf embryonne

    Energy Technology Data Exchange (ETDEWEB)

    Chapeville, F; Fromageot, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    It is shown that the formation of taurine from sulphate by the chicken embryo involves the reduction of sulphate to sulphite (I), the synthesis of cysteic acid (II) and its decarboxylation (Ill). The reaction (I) takes place in the vitellin sac. The reaction (II) results from the condensation of the sulphite with a-amino-acrylic acid and is carried out by the yolk. The enzymes responsible for the decarboxylation (III) are distributed both in the embryo and in its appendages. (author) [French] On demontre que la formation de taurine a partir de sulfate par l'embryon de poulet implique la reduction du sulfate en sulfite (1), la synthese de l'acide cysteique (Il) et sa decarboxylation (III). La reaction (I) a lieu dans le sac vitellin. La reaction (II) resulte de la condensation du sulfite avec l'acide a-amino-acrylique et est realisee par le jaune. Les enzymes assurant la decarboxylation (III) sont repartis aussi bien dans l'embryon que dans ses annexes. (auteur)

  9. 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

  10. Climate implications of carbonaceous aerosols: An aerosol microphysical study using the GISS/MATRIX climate model

    International Nuclear Information System (INIS)

    Bauer, Susanne E.; Menon, Surabi; Koch, Dorothy; Bond, Tami; Tsigaridis, Kostas

    2010-01-01

    Recently, attention has been drawn towards black carbon aerosols as a likely short-term climate warming mitigation candidate. However the global and regional impacts of the direct, cloud-indirect and semi-direct forcing effects are highly uncertain, due to the complex nature of aerosol evolution and its climate interactions. Black carbon is directly released as particle into the atmosphere, but then interacts with other gases and particles through condensation and coagulation processes leading to further aerosol growth, aging and internal mixing. A detailed aerosol microphysical scheme, MATRIX, embedded within the global GISS modelE includes the above processes that determine the lifecycle and climate impact of aerosols. This study presents a quantitative assessment of the impact of microphysical processes involving black carbon, such as emission size distributions and optical properties on aerosol cloud activation and radiative forcing. Our best estimate for net direct and indirect aerosol radiative forcing change is -0.56 W/m 2 between 1750 and 2000. However, the direct and indirect aerosol effects are very sensitive to the black and organic carbon size distribution and consequential mixing state. The net radiative forcing change can vary between -0.32 to -0.75 W/m 2 depending on these carbonaceous particle properties. Assuming that sulfates, nitrates and secondary organics form a coating shell around a black carbon core, rather than forming a uniformly mixed particles, changes the overall net radiative forcing from a negative to a positive number. Black carbon mitigation scenarios showed generally a benefit when mainly black carbon sources such as diesel emissions are reduced, reducing organic and black carbon sources such as bio-fuels, does not lead to reduced warming.

  11. Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

    Science.gov (United States)

    Wang, Junfeng; Ge, Xinlei; Chen, Yanfang; Shen, Yafei; Zhang, Qi; Sun, Yele; Xu, Jianzhong; Ge, Shun; Yu, Huan; Chen, Mindong

    2016-07-01

    In this work, the Aerodyne soot particle - aerosol mass spectrometer (SP-AMS) was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD) of China, for online characterization of the submicron aerosols (PM1). The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC) simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics). The average PM1 concentration was found to be 28.2 µg m-3, with organics (45 %) as the most abundant component, following by sulfate (19.3 %), nitrate (13.6 %), ammonium (11.1 %), rBC (9.7 %), and chloride (1.3 %). These PM1 species together can reconstruct ˜ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (cooking-related OA (COA), semi-volatile oxygenated OA (SV-OOA), and low-volatility oxygenated OA (LV-OOA). Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA) dominated the total OA mass (55.5 %), but primary organic aerosol (POA, equal to the sum of HOA and COA) can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand, in contrast to other species, sulfate, and LV-OOA concentrations increased in the afternoon, and showed no positive correlations with relative humidity (RH), likely indicating the contribution from photochemical oxidation is dominant over that of aqueous-phase processing for their formations. The

  12. 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.

  13. Optimization of the operation of packed bed bioreactor to improve the sulfate and metal removal from acid mine drainage.

    Science.gov (United States)

    Dev, Subhabrata; Roy, Shantonu; Bhattacharya, Jayanta

    2017-09-15

    The present study discusses the potentiality of using anaerobic Packed Bed Bioreactor (PBR) for the treatment of acid mine drainage (AMD). The multiple process parameters such as pH, hydraulic retention time (HRT), concentration of marine waste extract (MWE), total organic carbon (TOC) and sulfate were optimized together using Taguchi design. The order of influence of the parameters towards biological sulfate reduction was found to be pH > MWE > sulfate > HRT > TOC. At optimized conditions (pH - 7, 20% (v/v) MWE, 1500 mg/L sulfate, 48 h HRT and 2300 mg/L TOC), 98.3% and 95% sulfate at a rate of 769.7 mg/L/d. and 732.1 mg/L/d. was removed from the AMD collected from coal and metal mine, respectively. Efficiency of metal removal (Fe, Cu, Zn, Mg and Ni) was in the range of 94-98%. The levels of contaminants in the treated effluent were below the minimum permissible limits of industrial discharge as proposed by Bureau of Indian Standards (IS 2490:1981). The present study establishes the optimized conditions for PBR operation to completely remove sulfate and metal removal from AMD at high rate. The study also creates the future scope to develop an efficient treatment process for sulfate and metal-rich mine wastewater in a large scale. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Modeling of 2008 Kasatochi Volcanic Sulfate Direct Radiative Forcing: Assimilation of OMI SO2 Plume Height Data and Comparison with MODIS and CALIOP Observations

    Science.gov (United States)

    Wang, J.; Park, S.; Zeng, J.; Ge, C.; Yang, K.; Carn, S.; Krotkov, N.; Omar, A. H.

    2013-01-01

    Volcanic SO2 column amount and injection height retrieved from the Ozone Monitoring Instrument (OMI) with the Extended Iterative Spectral Fitting (EISF) technique are used to initialize a global chemistry transport model (GEOS-Chem) to simulate the atmospheric transport and lifecycle of volcanic SO2 and sulfate aerosol from the 2008 Kasatochi eruption, and to subsequently estimate the direct shortwave, top-of-the-atmosphere radiative forcing of the volcanic sulfate aerosol. Analysis shows that the integrated use of OMI SO2 plume height in GEOS-Chem yields: (a) good agreement of the temporal evolution of 3-D volcanic sulfate distributions between model simulations and satellite observations from the Moderate Resolution Imaging Spectroradiometer (MODIS) and Cloud-Aerosol Lidar with Orthogonal Polarisation (CALIOP), and (b) an e-folding time for volcanic SO2 that is consistent with OMI measurements, reflecting SO2 oxidation in the upper troposphere and stratosphere is reliably represented in the model. However, a consistent (approx. 25 %) low bias is found in the GEOS-Chem simulated SO2 burden, and is likely due to a high (approx.20 %) bias of cloud liquid water amount (as compared to the MODIS cloud product) and the resultant stronger SO2 oxidation in the GEOS meteorological data during the first week after eruption when part of SO2 underwent aqueous-phase oxidation in clouds. Radiative transfer calculations show that the forcing by Kasatochi volcanic sulfate aerosol becomes negligible 6 months after the eruption, but its global average over the first month is -1.3W/sq m, with the majority of the forcing-influenced region located north of 20degN, and with daily peak values up to -2W/sq m on days 16-17. Sensitivity experiments show that every 2 km decrease of SO2 injection height in the GEOS-Chem simulations will result in a approx.25% decrease in volcanic sulfate forcing; similar sensitivity but opposite sign also holds for a 0.03 m increase of geometric radius of

  15. Incorporation of 35S-sulfate and 3H-glucosamine into heparan and chondroitin sulfates during the cell cycle of B16-F10 cells

    International Nuclear Information System (INIS)

    Blair, O.C.; Sartorelli, A.C.

    1984-01-01

    Changes in glycosaminoglycan composition occurring during the cell cycle were determined in B16-F10 cells sorted flow cytometrically with respect to DNA content. Incorporation of 35 S-sulfate into heparan sulfate and chondroitin sulfate of unsorted and G1,S, and G2 +M sorted cells was determined following chondroitinase ABC or nitrous acid treatment; the incorporation into surface material was measured as the difference between the radioactivity of control and trypsin-treated cells. Incorporation of 35 S-sulfate and 3 H-glucosamine into cetyl pyridinium chloride (CPC)-precipitable material was characterized before and after chondroitinase or nitrous acid treatment by Sephadex G50 chromatography. Long-term (48 h) and short-term (1 h) labeling studies demonstrate that (a) the amount of total cellular chondroitin sulfate is greater than that of heparan sulfate, with larger amounts of unsulfated heparan than chondroitin being present; (b) the rate of turnover of heparan sulfate is greater than that of chondroitin sulfate; (c) greatest short-term incorporation of 3H-glucosamine into CPC-precipitable material occurs during S phase; and (d) the rate of turnover of both heparan sulfate and chondroitin sulfate is decreased in S phase relative to G1 and G2 + M

  16. Polarization behavior of new and used lead alloys in acid sulfate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, P.; O' Keefe, T.J. [Univ. of Missouri-Rolla, Materials Research Center and Dept. of Metallurgical Engineering, Rolla, Missouri (United States)

    2001-07-01

    Polarization and Electrochemical impedance were used to study various lead alloys commercially used to electrowin zinc and copper from acidic sulfate solutions. Anode specimens that had been in service at several electrowinning operations were tested and their electrochemical performance was compared to that obtained from new anode samples. Tests were conducted in sulfuric acid. Cyclic voltammetry was used in a potential range in which both Pb{sup +2} and Pb{sup +4} formed stable phases. Selected polarization tests were also made to study a number of variables, including changes in the concentration of cobalt and manganese in the electrolyte. Results showed that the phases formed on the surface of the anode were critical in defining the electrochemical behavior of the anodes. In particular, certain active phases, which were depolarizing were identified on some of the used anodes. It was possible to duplicate some of these phases in the laboratory. (author)

  17. Alleviating aluminum toxicity in an acid sulfate soil from Peninsular Malaysia by calcium silicate application

    Science.gov (United States)

    Elisa, A. A.; Ninomiya, S.; Shamshuddin, J.; Roslan, I.

    2016-03-01

    In response to human population increase, the utilization of acid sulfate soils for rice cultivation is one option for increasing production. The main problems associated with such soils are their low pH values and their associated high content of exchangeable Al, which could be detrimental to crop growth. The application of soil amendments is one approach for mitigating this problem, and calcium silicate is an alternative soil amendment that could be used. Therefore, the main objective of this study was to ameliorate soil acidity in rice-cropped soil. The secondary objective was to study the effects of calcium silicate amendment on soil acidity, exchangeable Al, exchangeable Ca, and Si content. The soil was treated with 0, 1, 2, and 3 Mg ha-1 of calcium silicate under submerged conditions and the soil treatments were sampled every 30 days throughout an incubation period of 120 days. Application of calcium silicate induced a positive effect on soil pH and exchangeable Al; soil pH increased from 2.9 (initial) to 3.5, while exchangeable Al was reduced from 4.26 (initial) to 0.82 cmolc kg-1. Furthermore, the exchangeable Ca and Si contents increased from 1.68 (initial) to 4.94 cmolc kg-1 and from 21.21 (initial) to 81.71 mg kg-1, respectively. Therefore, it was noted that calcium silicate was effective at alleviating Al toxicity in acid sulfate, rice-cropped soil, yielding values below the critical level of 2 cmolc kg-1. In addition, application of calcium silicate showed an ameliorative effect as it increased soil pH and supplied substantial amounts of Ca and Si.

  18. Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

    Science.gov (United States)

    Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

    2016-04-01

    Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

  19. Single-particle characterization of urban aerosol particles collected in three Korean cites using low-Z electron probe X-ray microanalysis.

    Science.gov (United States)

    Ro, Chul-Un; Kim, HyeKyeong; Oh, Keun-Young; Yea, Sun Kyung; Lee, Chong Bum; Jang, Meongdo; Van Grieken, René

    2002-11-15

    A recently developed single-particle analytical technique, called low-Z electron probe X-ray microanalysis (low-Z EPMA), was applied to characterize urban aerosol particles collected in three cities of Korea (Seoul, CheongJu, and ChunCheon) on single days in the winter of 1999. In this study, it is clearly demonstrated that the low-Z EPMA technique can provide detailed and quantitative information on the chemical composition of particles in the urban atmosphere. The collected aerosol particles were analyzed and classified on the basis of their chemical species. Various types of particles were identified, such as soil-derived, carbonaceous, marine-originated, and anthropogenic particles. In the sample collected in Seoul, carbonaceous, aluminosilicates, silicon dioxide, and calcium carbonate aerosol particles were abundantly encountered. In the CheongJu and ChunCheon samples, carbonaceous, aluminosilicates, reacted sea salts, and ammonium sulfate aerosol particles were often seen. However, in the CheongJu sample, ammonium sulfate particles were the most abundant in the fine fraction. Also, calcium sulfate and nitrate particles were significantly observed. In the ChunCheon sample, organic particles were the most abundant in the fine fraction. Also, sodium nitrate particles were seen at high levels. The ChunCheon sample seemed to be strongly influenced by sea-salt aerosols originating from the Yellow Sea, which is located about 115 km away from the city.

  20. Global volcanic aerosol properties derived from emissions, 1990-2014, using CESM1(WACCM): VOLCANIC AEROSOLS DERIVED FROM EMISSIONS

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Michael J. [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA; Schmidt, Anja [School of Earth and Environment, University of Leeds, Leeds UK; Easter, Richard [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Solomon, Susan [Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge Massachusetts USA; Kinnison, Douglas E. [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA; Ghan, Steven J. [Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Neely, Ryan R. [School of Earth and Environment, University of Leeds, Leeds UK; National Centre for Atmospheric Science, University of Leeds, Leeds UK; Marsh, Daniel R. [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA; Conley, Andrew [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA; Bardeen, Charles G. [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA; Gettelman, Andrew [Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder Colorado USA

    2016-03-06

    Accurate representation of global stratospheric aerosol properties from volcanic and non-volcanic sulfur emissions is key to understanding the cooling effects and ozone-loss enhancements of recent volcanic activity. Attribution of climate and ozone variability to volcanic activity is of particular interest in relation to the post-2000 slowing in the apparent rate of global average temperature increases, and variable recovery of the Antarctic ozone hole. We have developed a climatology of global aerosol properties from 1990 to 2014 calculated based on volcanic and non-volcanic emissions of sulfur sources. We have complied a database of volcanic SO2 emissions and plume altitudes for eruptions between 1990 and 2014, and a new prognostic capability for simulating stratospheric sulfate aerosols in version 5 of the Whole Atmosphere Community Climate Model, a component of the Community Earth System Model. Our climatology shows remarkable agreement with ground-based lidar observations of stratospheric aerosol optical depth (SAOD), and with in situ measurements of aerosol surface area density (SAD). These properties are key parameters in calculating the radiative and chemical effects of stratospheric