Dynamic-gravimetric preparation of metrologically traceable primary calibration standards for halogenated greenhouse gases

NASA Astrophysics Data System (ADS)

Guillevic, Myriam; Vollmer, Martin K.; Wyss, Simon A.; Leuenberger, Daiana; Ackermann, Andreas; Pascale, Céline; Niederhauser, Bernhard; Reimann, Stefan

2018-06-01

For many years, the comparability of measurements obtained with various instruments within a global-scale air quality monitoring network has been ensured by anchoring all results to a unique suite of reference gas mixtures, also called a primary calibration scale. Such suites of reference gas mixtures are usually prepared and then stored over decades in pressurised cylinders by a designated laboratory. For the halogenated gases which have been measured over the last 40 years, this anchoring method is highly relevant as measurement reproducibility is currently much better ( < 1 %, k = 2 or 95 % confidence interval) than the expanded uncertainty of a reference gas mixture (usually > 2 %). Meanwhile, newly emitted halogenated gases are already measured in the atmosphere at pmol mol-1 levels, while still lacking an established reference standard. For compounds prone to adsorption on material surfaces, it is difficult to evaluate mixture stability and thus variations in the molar fractions over time in cylinders at pmol mol-1 levels.To support atmospheric monitoring of halogenated gases, we create new primary calibration scales for SF6 (sulfur hexafluoride), HFC-125 (pentafluoroethane), HFO-1234yf (or HFC-1234yf, 2,3,3,3-tetrafluoroprop-1-ene), HCFC-132b (1,2-dichloro-1,1-difluoroethane) and CFC-13 (chlorotrifluoromethane). The preparation method, newly applied to halocarbons, is dynamic and gravimetric: it is based on the permeation principle followed by dynamic dilution and cryo-filling of the mixture in cylinders. The obtained METAS-2017 primary calibration scales are made of 11 cylinders containing these five substances at near-ambient and slightly varying molar fractions. Each prepared molar fraction is traceable to the realisation of SI units (International System of Units) and is assigned an uncertainty estimate following international guidelines (JCGM, 2008), ranging from 0.6 % for SF6 to 1.3 % (k = 2) for all other substances. The smallest uncertainty

Soil and litter exchange of reactive trace gases

EPA Science Inventory

The soil and litter play an important role in the exchange of trace gases between terrestrial ecosystems and the atmosphere. - The exchange of ammonia between vegetation and the atmosphere is highly influenced by soil and litter emissions especially in managed ecosystems (grassla...

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, Hann S.; Sather, Norman F.

1988-01-01

A process for reducing the amount of halogens and halogen acids in high temperature combustion gases and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Source gases: Concentrations, emissions, and trends

NASA Technical Reports Server (NTRS)

Fraser, Paul J.; Harriss, Robert; Penkett, Stuart A.; Makide, Yoshihiro; Sanhueza, Eugenio; Alyea, Fred N.; Rowland, F. Sherwood; Blake, Don; Sasaki, Toru; Cunnold, Derek M.

1991-01-01

Source gases are defined as those gases that influence levels of stratospheric ozone (O3) by transporting species containing halogen, hydrogen, and nitrogen to the stratosphere. Examples are the CFC's, methane (CH4), and nitrous oxide (N2O). Other source gases that also come under consideration in an atmospheric O3 context are those that are involved in the O3 or hydroxyl (OH) radical chemistry of the troposphere. Examples are CH4, carbon monoxide (CO), and nonmethane hydrocarbons (NMHC's). Most of the source gases, along with carbon dioxide (CO2) and water vapor (H2O), are climatically significant and thus affect stratospheric O3 levels by their influence on stratospheric temperatures. Carbonyl sulphide (COS) could affect stratospheric O3 through maintenance of the stratospheric sulphate aerosol layer, which may be involved in heterogeneous chlorine-catalyzed O3 destruction. The previous reviews of trends and emissions of source gases, either from the context of their influence on atmospheric O3 or global climate change, are updated. The current global abundances and concentration trends of the trace gases are given in tabular format.

Trace Gases, CO2, Climate, and the Greenhouse Effect.

ERIC Educational Resources Information Center

Aubrecht, Gordon J., II

1988-01-01

Reports carbon dioxide and other trace gases can be the cause of the Greenhouse Effect. Discusses some effects of the temperature change and suggests some solutions. Included are several diagrams, graphs, and a table. (YP)

Observations of halogenated trace gases in Taiwan and Malaysia

NASA Astrophysics Data System (ADS)

Gooch, Lauren J.; Laube, Johannes C.; Sturges, William T.; Oram, David E.; Wang, Jia-Lin; Ou-Yang, Cheng-Feng; Lin, Neng-Huei; Mead, Iq; Rigby, Matt; White, Emily

2015-04-01

There are a large variety of halocarbons present in the atmosphere that significantly impact on stratospheric ozone depletion and/or global warming. Though the use of some of these compounds has been phased out and replaced under global control measures, relatively long atmospheric lifetimes, imperfect substitutes and incomplete reductions in usage mean that global concentrations of halocarbons still require regular monitoring. This is especially true for the rapidly developing East Asian region, where high emissions have been repeatedly reported in recent years. We here present results from an air sampling activity in Taiwan and Malaysia during the spring months of 2013 and 2014. A large range of halocarbons, including a number of novel gases, were investigated via high sensitivity gas chromatography mass spectrometry (GC-MS). We find periods of relatively clean air as well as episodes that appear to be impacted by urban and/or industrial emissions and examine correlations between individual species. Observed mixing ratios are compared in context with both global background data and other regional studies. Enhancements in the abundances of many halocarbons are detected with examples including the Halons 1211 and 1202 as well as the very long-lived perfluorocarbons c-C4F8, C5F12 and C7F16. We also show and evaluate unusually high mixing ratios of other globally growing halocarbons such as sulphur hexafluoride (SF6), HCFC-133a (CF3CH2Cl), and CFC-113a (CF3CCl3). Finally, we use NAME analysis to produce back-trajectories in order to assess possible regional emission sources.

Halogenated source gases measured by FTIR at the Jungfraujoch station: updated trends and new target species

NASA Astrophysics Data System (ADS)

Mahieu, Emmanuel; Bader, Whitney; Bovy, Benoît; Franco, Bruno; Lejeune, Bernard; Servais, Christian; Notholt, Justus; Palm, Mathias; Toon, Geoffrey C.

2015-04-01

The atmospheric abundances of chlorine and fluorine increased very significantly during the second half of last century, following large emissions of long-lived halogenated source gases used in numerous industrial and domestic applications. Given the phase-out schedule of ozone depleting substances adopted by the Montreal Protocol, its Amendments and Adjustments, the loading of the CFCs in the Earth's atmosphere is now slowly decreasing. In contrast, their first replacement products, the HCFCs, are still on the rise, with current rates of increase substantially larger than at the beginning of the 21st century. As potent greenhouse gases, a suite of fluorinated compounds are targeted by the Kyoto Protocol. At present, they continue to accumulate in the atmosphere (Montzka et al., 2011). Given their environmental impacts, continuous monitoring of the abundances of these gases is of primary importance. In addition to the in situ networks, remote sensing techniques operated from space, balloon or from the ground provide valuable information to assess the long-term tropospheric and lower stratospheric trends of an increasing number of halogenated source gases, as well as of the reservoirs resulting from their photolysis in the stratosphere (e.g. Mahieu et al., 2014a). In this contribution, we will present decadal time series of halogenated source gases monitored at the high altitude station of the Jungfraujoch (46.5° N, 8° E, 3580 m asl) with Fourier Transform Infared (FTIR) spectrometers, within the framework of the Network for the Detection of Atmospheric Composition Change (NDACC, see http://www.ndacc.org). Total column trends presented in previous studies for CFC-11, -12 and HCFC-22 (Zander at al., 2008), CCl4 (Rinsland et al., 2012), HCFC-142b (Mahieu et al., 2013), CF4 (Mahieu et al., 2014b) and SF6 (Zander et al., 2008) will be updated using the latest available Jungfraujoch solar observations. Investigations dealing with the definition of approaches to

SI-traceable standards for atmospheric monitoring of halogenated gases

NASA Astrophysics Data System (ADS)

Guillevic, Myriam; Wyss, Simon A.; Pascale, Céline; Vollmer, Martin K.; Niederhauser, Bernhard; Reimann, Stefan

2017-04-01

To support atmospheric monitoring of greenhouse gases and in particular halogenated gases, we have developed a method to produce reference gas mixtures at nmol/mol (ppb) to pmol/mol levels (ppt). This method is dynamic and SI-traceable. This work is conducted in the framework of the EMRP projects HIGHGAS and KEY-VOCs as well as METAS' AtmoChemECV project. The method has been already applied to HFC-125 (pentafluoroethane, widely used in air conditioners), HFC-1234yf (2,3,3,3-tetrafluoropropene, a car air conditioner fluid of growing importance) and SF6 (insulant in electric switch-gears). It is currently being extended to HCFC-132b and CFC-13. It is particularly suitable for gas species and/or concentration ranges that are not stable in cylinders and it can be applied to a large variety of molecules related to air pollution and climate change (e.g., NO2, volatile organic compounds such as BTEX, NH3, water vapour at ppm level, CFCs, HCFCs, HFCs). The expanded uncertainty is less than 3 % (95 % confidence interval or k=2). The generation process is composed of four successive steps. In the first step the matrix gas, nitrogen or synthetic air is purified. Then this matrix gas is spiked with the pure substance, using a permeation device which contains a few grams of the pure substance (e.g., HFC-125) in the liquid form and loses it linearly over time by permeation through a membrane. This mass loss is precisely calibrated in our lab in Bern, using a magnetic suspension balance. In a third step the desired concentration is reached by dilution of the high concentration mixture exiting the permeation chamber with a chosen flow of the matrix gas in one or two subsequent dilution steps. All flows are piloted by mass flow controllers. All parts in contact with the gas mixture - including the balance - are passivated using coated surfaces, to reduce adsorption/desorption processes as much as possible. In the last step the mixture can be i) directly used to calibrate an

A search for biogenic trace gases in the atmosphere of Mars

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Mckay, Christopher P.

1989-01-01

The detection of certain trace gases in the atmosphere of Mars may serve as a possible indicator of microbial life on the surface of Mars. Candidate biogenic gases include methane CH4, ammonia NH3, nitrous oxide N2O, and several reduced sulfur species. Chemical thermodynamic equilibrium and photochemical calculations preclude the presence of these gases in any measurable concentrations in the atmosphere of Mars in the absence of biogenic production. A search for these gases utilizing either high resolution (spectral and spatial) spectroscopy from a Mars orbiter, such as the Observer, and or in situ measurements from a Mars lander or rover, is proposed.

CSIRO GASLAB Network: Individual Flask Measurements of Atmospheric Trace Gases (April 2003)

DOE Data Explorer

Steele, L. P. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Aspendale, Victoria, Australia; Krummel, P. R. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Aspendale, Victoria, Australia; Langenfelds, R. L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Aspendale, Victoria, Australia

2003-04-01

Data are available for four atmospheric trace gases at nine stationary sites and one moving platform (aircraft over Cape Grim, Tasmania, and Bass Strait, between the Australian continent and Tasmania). The trace gases are carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), and hydrogen (H2). Measurements of δ13C from CO2 are also included in this database. The nine stationary sites are, from north to south: Alert, Canada; Shetland Islands, Scotland; Estevan Point, Canada; Mauna Loa, Hawaii; Cape Ferguson, Australia; Cape Grim, Australia (Tasmania); Macquarie Island, Australia; Mawson, Antarctica; and the South Pole station, Antarctica.

Synthesis of observations of halogen-containing gases, ozone, and gaseous elemental mercury in the tropospheric plume of Redoubt Volcano, Alaska

NASA Astrophysics Data System (ADS)

Kelly, P. J.; Kern, C.; Lopez, T. M.; Werner, C. A.; Roberts, T. J.; Aiuppa, A.; Wang, B.

2011-12-01

Volcanoes are strong natural sources of halogen-containing acid gases and mercury. Most halogens are emitted from volcanoes as relatively non-reactive hydrogen halide gases, but recent field and modeling studies have shown that these species can be rapidly transformed into reactive forms via heterogeneous in-plume reactions. In order to further examine the chemical reactions that occur in volcanic plumes and their atmospheric impacts, we made ground and aircraft-based measurements of the composition of the tropospheric plume emitted from Redoubt Volcano, Alaska, which injected over 1 Tg of SO2, plus other gases and aerosols, into the subarctic free troposphere during 2009 and 2010. To our knowledge, our data include the first detailed study of ozone in a volcanic plume as well as the first measurements of HBr, HI, gaseous elemental mercury (GEM), and BrO in the plume of an Alaskan volcano. The composition of the plume was measured on June 20, 2010 using base-treated filter packs at the crater rim and by an instrumented fixed-wing aircraft on June 21 and August 19, 2010. The aircraft was used to track the chemical evolution of the plume up to ~30 km downwind (2 hours plume travel time) from the volcano. The airborne data from June 21 reveals rapid chemical ozone destruction in the plume as well as the strong influence chemical heterogeneity in background air had on plume composition. Airborne measurements on August 19 revealed several ppbv of ozone depletion near the center of the plume at a location ~5 km (20 minutes plume travel time) downwind and spectroscopic retrievals from traverses made under the plume show that BrO was present at a similar location. Simulations with the PlumeChem model reproduce the main features of the observed ozone deficits and evolution with time. The field measurements and model results suggest that autocatalytic release of reactive bromine and the formation of BrO can explain ozone destruction in the plume. Thus, volcanic eruptions in

Sources and sinks of trace gases in Amazonia and the Cerrado

Treesearch

M.M.C. Bustamante; Michael Keller; D.A. Silva

2009-01-01

Data for trace gas fluxes (NOx, N2O, and CH4) from the Amazon and cerrado region are presented with focus on the processes of production and consumption of these trace gases in soils and how they may be changed because of land use changes in both regions. Fluxes are controlled by seaonality, soil moisture, soil texture, topography, and fine-root dynamics. Compared to...

Monitoring trace gases in downtown Toronto using open-path Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

Byrne, B.; Strong, K.; Colebatch, O.; Fogal, P.; Mittermeier, R. L.; Wunch, D.; Jones, D. B. A.

2017-12-01

Emissions of greenhouse gases (GHGs) in urban environments can be highly heterogeneous. For example, vehicles produce point source emissions which can result in heterogeneous GHG concentrations on scales <10 m. The highly localized scale of these emissions can make it difficult to measure mean GHG concentrations on scales of 100-1000 m. Open-Path Fourier Transform Infrared Spectroscopy (OP-FTIR) measurements offer spatial averaging and continuous measurements of several trace gases simultaneously in the same airmass. We have set up an open-path system in downtown Toronto to monitor trace gases in the urban boundary layer. Concentrations of CO2, CO, CH4, and N2O are derived from atmospheric absorption spectra recorded over a two-way atmospheric open path of 320 m using non-linear least squares fitting. Using a simple box model and co-located boundary layer height measurements, we estimate surface fluxes of these gases in downtown Toronto from our OP-FTIR observations.

Aircraft measurements of trace gases between Japan and Singapore in October of 1993, 1996, and 1997

NASA Astrophysics Data System (ADS)

Matsueda, Hidekazu; Inoue, Hisayuki Y.

Carbon dioxide (CO2), methane (CH4), and carbon monoxide (CO) mixing ratios were measured in discrete air samples from aircraft between Japan and Singapore in October. The mixing ratios of all trace gases at 9-12 km were enhanced over the South China Sea in 1997 compared with those in 1993 and 1996. Vertical distributions of all trace gases over Singapore in 1997 also showed largely elevated mixing ratios at all altitudes. These distributions indicate a wide outflow of trace gases from intense biomass burning in the southeast Asia regions in the very strong El Niño year. The enhanced trace gases showed a strong linear correlation between CH4 and CO, and between CO and CO2, with the regression slopes of 0.051 (ΔCH4 ppb/ΔCOppb) and 0.089 (ΔCOppb/ΔCO2ppb). The emission ratios are characteristic of fires with relatively lower combustion efficiency from the tropical rain forest and peat lands in Kalimantan and Sumatra of Indonesia.

Long Term Association of Tropospheric Trace gases over Pakistan by exploiting satellite observations and development of Econometric Regression based Model

NASA Astrophysics Data System (ADS)

Zeb, Naila; Fahim Khokhar, Muhammad; Khan, Saud Ahmed; Noreen, Asma; Murtaza, Rabbia

2017-04-01

Air pollution is the expected key environmental issue of Pakistan as it is ranked among top polluted countries in the region. Ongoing rapid economic growth without any adequate measures is leading to worst air quality over time. The study aims to monitor long term atmospheric composition and association of trace gases over Pakistan. Tropospheric concentrations of CO, TOC, NO2 and HCHO derived from multiple satellite instruments are used for study from year 2005 to 2014. The study will provide first database for tropospheric trace gases over Pakistan. Spatio-temporal assessment identified hotspots and possible sources of trace gases over the Pakistan. High concentrations of trace gases are mainly observed over Punjab region, which may be attributed to its metropolitan importance. It is the major agricultural, industrialized and urbanized (nearly 60 % of the Pakistan's population) sector of the country. The expected sources are the agricultural fires, biomass/fossil fuel burning for heating purposes, urbanization, industrialization and meteorological variations. Seasonal variability is observed to explore seasonal patterns over the decade. Well defined seasonal cycles of trace gases are observed over the whole study period. The observed seasonal patterns also showed some noteworthy association among trace gases, which is further explored by different statistical tests. Seasonal Mann Kendall test is applied to test the significance of trend in series whereas correlation is carried out to measure the strength of association among trace gases. Strong correlation is observed for trace gases especially between CO and TOC. Partial Mann Kendall test is used to ideally identify the impact of each covariate on long term trend of CO and TOC by partialling out each correlating trace gas (covariate). It is observed that TOC, NO2 and HCHO has significant impact on long term trend of CO whereas, TOC critically depends on NO2 concentrations for long term increase over the region

Halogen and trace element geochemistry in Mid-Ocean Ridge basalts from the Australian-Antarctic Ridge (AAR)

NASA Astrophysics Data System (ADS)

Yang, Y. S.; Seo, J. H.; Park, S. H.; Kim, T.

2015-12-01

Australian-Antarctic Ridge (AAR) is an extension of easternmost SE Indian Mid-Ocean Ridge (MOR).We collected volcanic glasses from the "in-axis" of the KR1 and KR2 MOR, and the overlapping zones of the KR1 MOR and the nearby seamounts ("KR1 mixing"). We determined trace and halogen elements in the glasses. Halogen concentrations and its ratios in the glasses are important to understand the mantle metasomatism and volatile recycling. 52 of the collected glasses are "primitive" (higher than 6 wt% MgO), while 3 of them have rather "evolved" composition (MgO wt% of 1.72, 2.95 and 4.15). K2O concentrations and Th/Sc ratios in the glasses show a negative correlation with its MgO concentration. Incompatible element ratios such as La/Sm are rather immobile during a magma differentiation so the ratios are important to understand mantle composition (Hofmann et al. 2003). La/Sm ratios in the glasses are 0.95 ~ 3.28 suggesting that the AAR basalts can be classified into T-MORB and E-MORB (Schilling et al., 1983). La/Sm ratios are well-correlated with incompatible elements such as U, Ba, Nb, and negatively correlated with compatible elements such as Sc, Eu2+, Mg. The AAR glasses contain detectable halogen elements. The "KR1 mixing" glasses in halogen elements are more abundant than "in-axis" the glasses. Cl is the least variable element compared to the other halogens such as Br and I in the AAR. The "KR1 mixing" glasses have the largest variations of Br/Cl ratios compared to the "in-axis" glasses. The Cl/Br and Th/Sc ratios in the "in-axis" glasses and in the "KR1 mixing" glasses show positive and negative correlations, respectively. The Br-rich glasses in the "KR1 mixing" zone might be explained by a recycled Br-rich oceanic slab of paleo-subduction or by a hydrothermal alteration in the AAR. I composition in the glasses does not show a correlation other trace elements. The K/Cl and K/Ti ratios in the AAR glasses are similar to the basalts from the Galapagos Spreading Center

Long-Term Changes of Tropospheric Trace Gases over Pakistan Derived From Multiple Satellite Instruments

NASA Astrophysics Data System (ADS)

Zeb, Naila; Fahim Khokhar, Muhammad; Murtaza, Rabbia; Noreen, Asma; Khalid, Tameem

2016-07-01

Air pollution is the expected key environmental issue of Pakistan in coming years due to its ongoing rapid economic growth and this trend suggests only worst air quality over time. In 2014, World bank reported the Pakistan's urban air quality among the most severe in the world and intimated the government to make improvement in air quality as a priority policy agenda. In addition it is recommended to strengthen the institutional and technical capacity of organizations responsible for air quality management. Therefore, the study is designed to put efforts in highlighting air quality issues. The study will provide first database for tropospheric trace gases over Pakistan. The study aims to analyse tropospheric concentrations of CO, TOC, NO2 and HCHO over Pakistan using multisensory data from January 2005 to January 2014. Spatio-temporal and seasonal variability of tropospheric trace gases is observed over the decade to explore long term trend. Hotspots are identified to see variation of species with latitude and to highlight possible sources of trace gases over the Pakistan. High concentrations of trace gases are mainly observed over the Punjab region, which may be attributed to its metropolitan importance. It is the major agricultural, industrialized and urbanized (nearly 60% of the Pakistan's population) sector of the country. Overall significant decreasing trend of CO is identified by MOPITT with relative change of 12.4%. Tropospheric ozone column (TOC) showed insignificant increasing trend with temporal increase of 10.4% whereas NO2 exhibited a significant temporal increase of about 28%. For formaldehyde (HCHO), an increase of about 3.8% is calculated for SCIAMACHY data. Well defined seasonal cycles for these trace gases are observed over the whole study period. CO concentrations showed peak in winter months (November/December/January/February) and dip in the months of Summer/Monsoon (June/July/August). In spite of CO, TCO increases gradually in March and peaks

Evolution of trace gases and particles emitted by a chaparral fire in California

Treesearch

S. K. Akagi; J. S. Craven; J. W. Taylor; G. R. McMeeking; R. J. Yokelson; I. R. Burling; S. P. Urbanski; C. E. Wold; J. H. Seinfeld; H. Coe; M. J. Alvarado; D. R. Weise

2012-01-01

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November...

Tropospheric Halogen Chemistry

NASA Astrophysics Data System (ADS)

von Glasow, R.; Crutzen, P. J.

2003-12-01

processes. Early work by Cauer (1951) had shown that Cl/Na and Cl/Mg ratios were lower in air than in seawater, indicating loss of chlorine by "acid displacement" from sea salt by the strong acids, H2SO4 (Eriksson (1959a, b) and HNO3 (Robbins et al., 1959). Already the first measurements of bromine in aerosols by Duce et al. (1963) showed that bromine, like chlorine, was lost from the sea salt particles, whereas iodine was strongly enriched ( Duce et al., 1965). Research since the early 1980s has shown that photochemical processes are actively involved.Interest in the chemistry of atmospheric halogens took a steep upward surge after it was postulated that the release of industrially produced halocarbons, in particular the chlorofluorocarbons (CFCs), CFCl3, and CF2Cl2, could cause severe depletions in stratospheric ozone (Molina and Rowland, 1974) by the reactions involving the CFC photolytic product radicals, Cl and ClO, as catalysts. The first stratospheric measurements of ClO did indeed show its presence in significant quantities in the stratosphere so that by the end of the 1970s USA, Canada, and the Scandinavian countries issued laws against the use of CFC gases as propellants in spray cans. In the mid-1980s the springtime stratospheric ozone hole over Antarctica was discovered by Farman et al. (1985), involving heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation ( Solomon et al., 1986). Ten years later, in 1996, a complete phaseout ofthe production of the CFCs and a number of other chlorine- or bromine-containing chemicals came into effect for all nations in the developed world. In this contribution we will, however, concentrate on the impact of reactive chlorine, bromine, and iodine on tropospheric ozone chemistry.Halogens have the potential to be important in many facets of tropospheric chemistry. A multitude of gas phase reactions and gas-particle interactions occur that include coupling with the sulfur cycle and reactions with

Halogen Containing Gases as Lubricants for Crystallized Glass Ceramic Metal Combinations at Temperatures to 1500 F

NASA Technical Reports Server (NTRS)

Buckley, Donald H.; Johnson, Robert L.

1960-01-01

Pyroceram 9608 (a crystallized glass ceramic) has been considered for use in high-temperature bearing and seal applications. One of the problems encountered with Pyroceram is the lack of availability of lubricants for the temperature range in which this material becomes practical. Experiments were conducted with Pyroceram sliding on various nickel- and cobalt-base alloys using reactive halogen-containing gases as lubricants. Friction and wear data were obtained as a function of sliding velocity and temperature. Studies were made with a hemispherical rider (3/16-in. rad., Pyroceram 9608) sliding in a circumferential path on the flat surface of a rotating disk (2(1/2) in. diam., nickel- or cobalt-base alloys). The specimens were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 3200 feet per minute, and temperatures from 75 to 1500 F. The gas CF2Br-CF2Br was found to be an effective lubricant for Pyroceram 9608 sliding on Hastelloy R-235 and Inconel X up to 1400 F. The gas CF2Cl-CF2Cl provided effective lubrication for Pyroceram sliding on various cobalt-base alloys at 1000 F.

Pilot Institute on Global Change on Trace Gases and the Biosphere, 1988

NASA Technical Reports Server (NTRS)

Eddy, J. A.; Moore, B.

1998-01-01

Table of Contents: Summary; Background; General Framework for a Series of Institutes on Global Change; The 1988 Pilot Institute on Global Changes: Trace Gases and the Biosphere; Budget; List of Acronyms; and Attachments.

Method for detecting trace impurities in gases

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Holland, Redus F.; Beattie, Willard H.

1981-01-01

A technique for considerably improving the sensitivity and specificity of infrared spectrometry as applied to quantitative determination of trace impurities in various carrier or solvent gases is presented. A gas to be examined for impurities is liquefied and infrared absorption spectra of the liquid are obtained. Spectral simplification and number densities of impurities in the optical path are substantially higher than are obtainable in similar gas-phase analyses. Carbon dioxide impurity (.about.2 ppm) present in commercial Xe and ppm levels of Freon 12 and vinyl chloride added to liquefied air are used to illustrate the method.

Method for detecting trace impurities in gases

DOEpatents

Freund, S.M.; Maier, W.B. II; Holland, R.F.; Beattie, W.H.

A technique for considerably improving the sensitivity and specificity of infrared spectrometry as applied to quantitative determination of trace impurities in various carrier or solvent gases is presented. A gas to be examined for impurities is liquefied and infrared absorption spectra of the liquid are obtained. Spectral simplification and number densities of impurities in the optical path are substantially higher than are obtainable in similar gas-phase analyses. Carbon dioxide impurity (approx. 2 ppM) present in commercial Xe and ppM levels of Freon 12 and vinyl chloride added to liquefied air are used to illustrate the method.

Greenhouse effect of chlorofluorocarbons and other trace gases

NASA Technical Reports Server (NTRS)

Hansen, James; Lacis, Andrew; Prather, Michael

1989-01-01

A comparison is made of the radiative (greenhouse) forcing of the climate system due to changes of atmospheric chlorofluorocarbons and other trace gases. It is found that CFCs, defined to include chlorofluorocarbons, chlorocarbons, and fluorocarbons, now provide about one-quater of current annual increases in anthropogenic greenhouse climate forcing. If the growth rates of CFC production in the early 1970s had continued to the present, current annual growth of climate forcing due to CFCs would exceed that due to CO2.

Epiphytic cryptogams as a source of bioaerosols and trace gases

NASA Astrophysics Data System (ADS)

Ruckteschler, Nina; Hrabe de Angelis, Isabella; Zartman, Charles E.; Araùjo, Alessandro; Pöschl, Ulrich; Manzi, Antonio O.; Andreae, Meinrat O.; Pöhlker, Christopher; Weber, Bettina

2016-04-01

Cryptogamic covers comprise (cyano-)bacteria, algae, lichens, bryophytes, fungi, and archaea in varying proportions. These organisms do not form flowers, but reproduce by spores or cell cleavage with these reproductive units being dispersed via the atmosphere. As so-called poikilohydric organisms they are unable to regulate their water content, and their physiological activity pattern mainly follows the external water conditions. We hypothesize, that both spore dispersal and the release of trace gases are governed by the moisture patterns of these organisms and thus they could have a greater impact on the atmosphere than previously thought. In order to test this hypothesis, we initiated experiments at the study site Amazonian Tall Tower Observatory (ATTO) in September 2014. We installed microclimate sensors in epiphytic cryptogams at four different heights of a tree to monitor the activity patterns of these organisms. Self-developed moisture probes are used to analyze the water status of the organisms accompanied by light and temperature sensors. The continuously logged data are linked to ongoing measurements of trace gases and particulate bioaerosols to analyze these for the relevance of cryptogams. Here, we are particularly interested in diurnal cycles of coarse mode particles and the atmospheric abundance of fine potassium-rich particles from a currently unknown biogenic source. Based upon the results of this field study we also investigate the bioaerosol and trace gas release patterns of cryptogamic covers under controlled conditions. With this combined approach of field and laboratory experiments we aim to disclose the role of cryptogamic covers in bioaerosol and trace gas release patterns in the Amazonian rainforest.

Climate-chemical interactions and effects of changing atmospheric trace gases

NASA Technical Reports Server (NTRS)

Ramanathan, V.; Callis, L.; Cess, R.; Hansen, J.; Isaksen, I.

1987-01-01

The paper considers trace gas-climate effects including the greenhouse effect of polyatomic trace gases, the nature of the radiative-chemical interactions, and radiative-dynamical interactions in the stratosphere, and the role of these effects in governing stratospheric climate change. Special consideration is given to recent developments in the investigations of the role of oceans in governing the transient climate responses, and a time-dependent estimate of the potential trace gas warming from the preindustrial era to the early 21st century. The importance of interacting modeling and observational efforts is emphasized. One of the problems remaining on the observational front is the lack of certainty in current estimates of the rate of growth of CO, O3, and NOx; the primary challenge is the design of a strategy that will minimize the sampling errors.

Gas phase acid, ammonia and aerosol ionic and trace element concentrations at Cape Verde during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) 2007 intensive sampling period

NASA Astrophysics Data System (ADS)

Sander, R.; Pszenny, A. A. P.; Keene, W. C.; Crete, E.; Deegan, B.; Long, M. S.; Maben, J. R.; Young, A. H.

2013-07-01

We report mixing ratios of soluble reactive trace gases sampled with mist chambers and the chemical composition of bulk aerosol and volatile inorganic bromine (Brg) sampled with filter packs during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) field campaign at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente island in the tropical North Atlantic in May and June 2007. The gas-phase data include HCl, HNO3, HONO, HCOOH, CH3COOH, NH3, and volatile reactive chlorine other than HCl (Cl*). Aerosol samples were analyzed by neutron activation (Na, Al, Cl, V, Mn, and Br) and ion chromatography (SO42-, Cl-, Br-, NH4+, Na+, K+, Mg2+, and Ca2+). Content and quality of the data, which are available under doi:10.5281/zenodo.6956, are presented and discussed.

Gas phase acid, ammonia and aerosol ionic and trace element concentrations at Cape Verde during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) 2007 intensive sampling period

NASA Astrophysics Data System (ADS)

Sander, R.; Pszenny, A. A. P.; Keene, W. C.; Crete, E.; Deegan, B.; Long, M. S.; Maben, J. R.; Young, A. H.

2013-12-01

We report mixing ratios of soluble reactive trace gases sampled with mist chambers and the chemical composition of bulk aerosol and volatile inorganic bromine (Brg) sampled with filter packs during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) field campaign at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente island in the tropical North Atlantic in May and June 2007. The gas-phase data include HCl, HNO3, HONO, HCOOH, CH3COOH, NH3, and volatile reactive chlorine other than HCl (Cl*). Aerosol samples were analyzed by neutron activation (Na, Al, Cl, V, Mn, and Br) and ion chromatography (SO42-, Cl-, Br-, NH4+, Na+, K+, Mg2+, and Ca2+). Content and quality of the data, which are available under doi:10.5281/zenodo.6956, are presented and discussed.

Monitoring shipping emissions with MAX-DOAS measurements of reactive trace gases

NASA Astrophysics Data System (ADS)

Wittrock, Folkard; Peters, Enno; Seyler, André; Kattner, Lisa; Mathieu-Üffing, Barbara; Burrows, John P.; Chirkov, Maksym; Meier, Andreas C.; Richter, Andreas; Schönhardt, Anja; Schmolke, Stefan; Theobald, Norbert

2014-05-01

Air pollution from ships contributes to overall air quality problems and it has direct health effects on the population in particular in coastal regions, and in harbor cities. In order to reduce the emissions the International Maritime Organisation (IMO) have tightened the regulations for air pollution. E.g. Sulfur Emission Control Areas (SECA) have been introduced where the sulfur content of marine fuel is limited. However, up to now there is no regular monitoring system available to verify that ships are complying with the new regulations. Furthermore measurements of reactive trace gases in marine environments are in general sparse. The project MeSMarT (Measurements of shipping emissions in the marine troposphere, www.mesmart.de) has been established as a cooperation between the University of Bremen and the German Bundesamt für Seeschifffahrt und Hydrographie (Federal Maritime and Hydrographic Agency) with support of the Helmholtz Research Centre Geesthacht to estimate the influence of ship emissions on the chemistry of the atmospheric boundary layer and to establish a monitoring system for main shipping routes. Here we present MAX-DOAS observations of NO2 and SO2 carried out during ship campaigns in the North and Baltic Sea and from two permanent sites close to the Elbe river (Wedel, Germany) and on the island Neuwerk close to the mouths of Elbe and Weser river. Mixing ratios of both trace gases have been retrieved using different approaches (pure geometric and taking into account the radiative transfer) and compared to in situ and air borne observations (see Kattner et al., Monitoring shipping emissions with in-situ measurements of trace gases, and Meier et al., Airborne measurements of NO2 shipping emissions using imaging DOAS) observations. Furthermore simple approaches have been used to calculate emission factors of NOx and SO2 for single ships.

Long-term Studies of Marine Halogen Release

NASA Astrophysics Data System (ADS)

Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

2009-04-01

Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

A measurement system for the atmospheric trace gases CH4 and CO

NASA Technical Reports Server (NTRS)

Condon, E. P.

1977-01-01

A system for measuring ambient clean air levels of the atmospheric trace gases methane and carbon monoxide is described. The analytical method consists of a gas chromatographic technique that incorporates sample preconcentration with catalytic conversion of CO to CH4 and subsequent flame ionization detection of these gases. The system has sufficient sensitivity and repeatability to make the precise measurements required to establish concentration profiles for CO and CH4 in the planetary boundary layer. A discussion of the bottle sampling program being conducted to obtain the samples for the concentration profiles is also presented.

Survey of Instrumentation for the Measurement of Stratospheric Trace Gases and Particulates (CIAP)

DOT National Transportation Integrated Search

1971-11-01

A survey was conducted to determine the applicability of presently available instrumentation to the direct and/or remote measure of trace gases and particulates within the stratosphere. Consideration was also given to techniques under development whe...

Quantifying sources and sinks of trace gases using space-borne measurements: current and future science.

PubMed

Palmer, Paul I

2008-12-28

We have been observing the Earth's upper atmosphere from space for several decades, but only over the past decade has the necessary technology begun to match our desire to observe surface air pollutants and climate-relevant trace gases in the lower troposphere, where we live and breathe. A new generation of Earth-observing satellites, capable of probing the lower troposphere, are already orbiting hundreds of kilometres above the Earth's surface with several more ready for launch or in the planning stages. Consequently, this is one of the most exciting times for the Earth system scientists who study the countless current-day physical, chemical and biological interactions between the Earth's land, ocean and atmosphere. First, I briefly review the theory behind measuring the atmosphere from space, and how these data can be used to infer surface sources and sinks of trace gases. I then present some of the science highlights associated with these data and how they can be used to improve fundamental understanding of the Earth's climate system. I conclude the paper by discussing the future role of satellite measurements of tropospheric trace gases in mitigating surface air pollution and carbon trading.

Mid-Infrared OPO for High Resolution Measurements of Trace Gases in the Mars Atmosphere

NASA Technical Reports Server (NTRS)

Yu, Anthony W.; Numata,Kenji; Riris, haris; Abshire, James B.; Allan, Graham; Sun, Xiaoli; Krainak, Michael A.

2008-01-01

The Martian atmosphere is composed primarily (>95%) of CO2 and N2 gas, with CO, O2, CH4, and inert gases such as argon comprising most of the remainder. It is surprisingly dynamic with various processes driving changes in the distribution of CO2, dust, haze, clouds and water vapor on global scales in the meteorology of Mars atmosphere [I]. The trace gases and isotopic ratios in the atmosphere offer important but subtle clues as to the origins of the planet's atmosphere, hydrology, geology, and potential for biology. In the search for life on Mars, an important process is the ability of bacteria to metabolize inorganic substrates (H2, CO2 and rock) to derive energy and produce methane as a by-product of anaerobic metabolism. Trace gases have been measured in the Mars atmosphere from Earth, Mars orbit, and from the Mars surface. The concentration of water vapor and various carbon-based trace gases are observed in variable concentrations. Within the past decade multiple groups have reported detection of CH4, with concentrations in the 10's of ppb, using spectroscopic observations from Earth [2]. Passive spectrometers in the mid-infrared (MIR) are restricted to the sunlit side of the planet, generally in the mid latitudes, and have limited spectral and spatial resolution. To accurately map the global distribution and to locate areas of possibly higher concentrations of these gases such as plumes or vents requires an instrument with high sensitivity and fine spatial resolution that also has global coverage and can measure during both day and night. Our development goal is a new MIR lidar capable of measuring, on global scales, with sensitivity, resolution and precision needed to characterize the trace gases and isotopic ratios of the Martian atmosphere. An optical parametric oscillator operating in the MIR is well suited for this instrument. The sufficient wavelength tuning range of the OPO can extend the measurements to other organic molecules, CO2, atmospheric water

Halogen bond: a long overlooked interaction.

PubMed

Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

2015-01-01

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

Improved aqueous scrubber for collection of soluble atmospheric trace gases

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Talbot, R. W.; Collins, V. G.

1985-01-01

A new concentration technique for the extraction and enrichment of water-soluble atmospheric trace gases has been developed. The gas scrubbing technique efficiently extracts soluble gases from a large volume flow rate of air sample into a small volume of refluxed trapping solution. The gas scrubber utilizes a small nebulizing nozzle that mixes the incoming air with an aqueous extracting solution to form an air/droplet mist. The mist provides excellent interfacial surface areas for mass transfer. The resulting mist sprays upward through the reaction chamber until it impinges upon a hydrophobic membrane that virtually blocks the passage of droplets but offers little resistance to the existing gas flow. Droplets containing the scrubbed gases coalesce on the membrane and drip back into the reservoir for further refluxing. After a suitable concentration period, the extracting solution containing the analyte can be withdrawn for analysis. The nebulization-reflex concentration technique is more efficient (maximum flow of gas through the minimum volume of extractant) than conventional bubbler/impinger gas extraction techniques and is offered as an alternative method.

Interaction of acidic trace gases with ice from a surface science perspective

NASA Astrophysics Data System (ADS)

Waldner, A.; Kong, X.; Ammann, M.; Orlando, F.; Birrer, M.; Artiglia, L.; Bartels-Rausch, T.

2016-12-01

Acidic trace gases, such as HCOOH, HCl and HONO, play important roles in atmospheric chemistry. The presence of ice is known to have the capability to modify this chemistry (Neu et al. 2012). The molecular level processes of the interaction of acidic trace gases with ice are still a matter of debate and a quantification of the uptake is difficult (Dash et al. 2006, Bartels-Rausch et al. 2014, Huthwelker et al. 2006). This hampers a proper inclusion of ice as a substrate in models of various scales as for example in global chemistry climate models that would among others allow predicting large-scale effects of ice clouds. So far, direct observations of the ice surface and of the interaction with trace gases at temperatures and concentrations relevant to the environment are very limited. In this study, we take advantage of the surface and analytical sensitivity as well as the chemical selectivity of photoemission and absorption spectroscopy performed at ambient pressure using the near ambient pressure photoemission endstation (NAPP) at Swiss Light Source to overcome this limitation in environmental science (Orlando et al. 2016). Specifically, ambient pressure X-ray Photoelectron Spectroscopy (XPS) allows us to get information about chemical state and concentration depth profiles of dopants. The combination of XPS with auger electron yield Near-Edge X-ray Absorption Fine Structure (NEXAFS) enables us to locate the dopant and analyse wheather the interaction leads to enhanced surface disorder and to what extent different disorders influences the uptake of the trace gas. For the first time, this study looks directly at the interaction of HCOOH, the strongest organic acid, with ice at 2 different temperatures (233 and 253 K) relevant for environmental science by means of electron spectroscopy. XPS depth profiles indicate that the HCOOH basically remains within the topmost ice layers and O K-edge NEXAFS analysis show that the interaction ice-HCOOH does not lead to

Sensitivity of RF-driven Plasma Filaments to Trace Gases

NASA Astrophysics Data System (ADS)

Burin, M. J.; Czarnocki, C. J.; Czarnocki, K.; Zweben, S. J.; Zwicker, A.

2011-10-01

Filamentary structures have been observed in many types of plasma discharges in both natural (e.g. lightning) and industrial systems (e.g. dielectric barrier discharges). Recent progress has been made in characterizing these structures, though various aspects of their essential physics remain unclear. A common example of this phenomenon can be found within a toy plasma globe (or plasma ball), wherein a primarily neon gas mixture near atmospheric pressure clearly and aesthetically displays filamentation. Recent work has provided the first characterization of these plasma globe filaments [Campanell et al., Physics of Plasmas 2010], where it was noticed that discharges of pure gases tend not to produce filaments. We have extended this initial work to investigate in greater detail the dependence of trace gases on filamentation within a primarily Neon discharge. Our preliminary results using a custom globe apparatus will be presented, along with some discussion of voltage dependencies. Newly supported by the NSF/DOE Partnership in Basic Plasma Science and Engineering.

Tracking Oxidation During Transport of Trace Gases in Air from the Northern to Southern Hemisphere

NASA Astrophysics Data System (ADS)

Montzka, S. A.; Moore, F. L.; Atlas, E. L.; Parrish, D. D.; Miller, B. R.; Sweeney, C.; McKain, K.; Hall, B. D.; Siso, C.; Crotwell, M.; Hintsa, E. J.; Elkins, J. W.; Blake, D. R.; Barletta, B.; Meinardi, S.; Claxton, T.; Hossaini, R.

2017-12-01

Trace gas mole fractions contain the imprint of recent influences on an air mass such as sources, transport, and oxidation. Covariations among the many gases measured from flasks during ATom and HIPPO, and from the ongoing NOAA cooperative air sampling program enable recent influences to be identified from a wide range of sources including industrial activity, biomass burning, emissions from wetlands, and uptake by terrestrial ecosystems. In this work we explore the evolution of trace gas concentrations owing to atmospheric oxidation as air masses pass through the tropics, the atmospheric region with the highest concentrations of the hydroxyl radical. Variations in C2-C5 hydrocarbon concentrations downwind of source regions provide a measure of photochemical ageing in an air mass since emission, but they become less useful when tracking photochemical ageing as air is transported from the NH into the SH owing to their low mixing ratios, lifetimes that are very short relative to transport times, non-industrial sources in the tropics (e.g., biomass burning), and southern hemispheric sources. Instead, we consider a range of trace gases and trace gas pairs that provide a measure of photochemical processing as air transits the tropics. To be useful in this analysis, these trace gases would have lifetimes comparable to interhemispheric transport times, emissions arising from only the NH at constant relative magnitudes, and concentrations sufficient to allow precise and accurate measurements in both hemispheres. Some anthropogenically-emitted chlorinated hydrocarbons meet these requirements and have been measured during ATom, HIPPO, and from NOAA's ongoing surface sampling efforts. Consideration of these results and their implications for tracking photochemical processing in air as it is transported across the tropics will be presented.

CO2 lidar for measurements of trace gases and wind velocities

NASA Technical Reports Server (NTRS)

Hess, R. V.

1982-01-01

CO2 lidar systems technology and signal processing requirements relevant to measurement needs and sensitivity are discussed. Doppler processing is similar to microwave radar, with signal reception controlled by a computer capable of both direct and heterodyne operations. Trace gas concentrations have been obtained with the NASA DIAL system, and trace gas transport has been determined with Doppler lidar measurements for wind velocity and turbulence. High vertical resolution measurement of trace gases, wind velocity, and turbulence are most important in the planetary boundary layer and in regions between the PBL and the lower stratosphere. Shear measurements are critical for airport operational safety. A sensitivity analysis for heterodyne detection with the DIAL system and for short pulses using a Doppler lidar system is presented. The development of transient injection locking techniques, as well as frequency stability by reducing chirp and catalytic control of closed cycle CO2 laser chemistry, is described.

Opo lidar sounding of trace atmospheric gases in the 3 - 4 μm spectral range

NASA Astrophysics Data System (ADS)

Romanovskii, Oleg A.; Sadovnikov, Sergey A.; Kharchenko, Olga V.; Yakovlev, Semen V.

2018-04-01

The applicability of a KTA crystal-based laser system with optical parametric oscillators (OPO) generation to lidar sounding of the atmosphere in the spectral range 3-4 μm is studied in this work. A technique developed for lidar sounding of trace atmospheric gases (TAG) is based on differential absorption lidar (DIAL) method and differential optical absorption spectroscopy (DOAS). The DIAL-DOAS technique is tested to estimate its efficiency for lidar sounding of atmospheric trace gases. The numerical simulation performed shows that a KTA-based OPO laser is a promising source of radiation for remote DIAL-DOAS sounding of the TAGs under study along surface tropospheric paths. A possibility of using a PD38-03-PR photodiode for the DIAL gas analysis of the atmosphere is shown.

Unexpected autumnal halogen activity in the lower troposphere at Neumayer III/Antarctica

NASA Astrophysics Data System (ADS)

Nasse, Jan-Marcus; Frieß, Udo; Pöhler, Denis; Schmitt, Stefan; Weller, Rolf; Schaefer, Thomas; Platt, Ulrich

2017-04-01

The influence of Reactive Halogen Species (RHS, like IO, BrO, ClO, etc.) on the lower polar troposphere has been subject of intense research for several decades. Ozone Depletion Events (ODEs) caused by the catalytic reaction of tropospheric ozone with inorganic halogen species or the oxidation of gaseous elemental mercury are well observed phenomena that occur during the respective springtime in both Arctic and Antarctica. Chlorine atoms also react more efficiently with hydrocarbons than e.g. OH radicals and all reactive halogen species can furthermore influence the atmospheric sulphur or nitrate cycles. While an autocatalytic release mechanism from salty surfaces, the so called bromine explosion, has been identified to rapidly increase inorganic bromine mixing ratios many aspects of atmospheric halogen chemistry in polar regions remains unclear. Since January 2016, we are operating an active Long Path DOAS instrument at Neumayer III on the Antarctic Ekström shelf ice designed for autonomous measurements. This instrument is able to detect a wide range of trace gases absorbing in the UV/Vis including ClO, BrO, OClO, IO, I2, OIO, ozone, NO2, H2O, O4, and SO2 at a temporal resolution of 5-30 minutes. The analysis of the first year of observations shows several surprising findings which give new insights into polar halogen chemistry. E.g. we observe surprisingly strong bromine activity in late summer and autumn (in addition to well-known springtime events) with mixing ratios often higher than 20 pptv. We could even observe peak mixing ratios of 110 pptv. The observed BrO levels could be the result of local/regional chemistry rather than long-range transport and modulated by the stability of the boundary layer. Also, there are hints for NOx - driven halogen activation. Furthermore, chlorine monoxide (ClO) and OClO mixing ratios of several ten pptv could be detected on a number of days, however the source mechanism for reactive chlorine remains unclear. We will give an

The effects of biomass burning on the concentration of trace gases in the atmosphere

NASA Technical Reports Server (NTRS)

Donaldson, Leon M.

1988-01-01

Over the past several years, there has been considerable interest concerning the global effects of biomass burning on concentrations of trace gases in the atmosphere. The paucity of reported studies and investigations into the effects of the Greenhouse Gases such as carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), up until about a decade ago, would suggest that the topic was not then one of universal concern. Efforts are now being made to understand the biogenic, anthropogenic and photochemical sources of atmospheric trace gases. Biomass burning which includes the burning of forests for clearing, the burning of vegetative stubble after harvesting, and lightning and human-induced wildfires is but one consideration under the general paradigm of atmospheric perturbations. A team of researchers from the Langley Research Center, along with the Canadian Forest Ministry, Ontario, Canada collaborated in an experiment in a deforestration effort through a prescribed burn. Through a specially designed experimental modeling and instrumentation, a substantial pre-burn data set was collected. The primary focus of the pre-burn experimental activities was the emission of nitrous oxide (N2O) gas from selected sites.

Mobile Platforms for Continuous Spatial Measurements of Urban Trace Gases and Criteria Pollutants

NASA Astrophysics Data System (ADS)

Fasoli, B.; Mitchell, L.; Bares, R.; Crosman, E.; Bush, S. E.; Horel, J.; Lin, J. C.; Bowling, D. R.; Ehleringer, J. R.

2015-12-01

Surface-based observations of atmospheric trace gases and criteria pollutants provide critical data on how emissions and pollutant concentrations vary over time. However, traditional stationary measurement sites only quantify concentrations at a single point in space, limiting our ability to understand spatial patterns. Using trace gas instrumentation capable of making continuous high-frequency (~1s) measurements, we have developed mobile platforms to complement stationary observation sites in order to better constrain the heterogeneity and complexities of urban emissions. These compact trace gas and criteria pollutant measurement systems are capable of precisely measuring CO2, CH4 PM2.5, O3, NOx, and several meteorological parameters on TRAX, Salt Lake City's light-rail system, and in a van-based mobile laboratory. Using case study observations, we discuss mobile measurement methodologies and the practical applications of mobile trace gas sampling platforms.

Anesthetic gases and global warming: Potentials, prevention and future of anesthesia.

PubMed

Gadani, Hina; Vyas, Arun

2011-01-01

Global warming refers to an average increase in the earth's temperature, which in turn causes changes in climate. A warmer earth may lead to changes in rainfall patterns, a rise in sea level, and a wide range of impacts on plants, wildlife, and humans. Greenhouse gases make the earth warmer by trapping energy inside the atmosphere. Greenhouse gases are any gas that absorbs infrared radiation in the atmosphere and include: water vapor, carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), halogenated fluorocarbons (HCFCs), ozone (O3), perfluorinated carbons (PFCs), and hydrofluorocarbons (HFCs). Hazardous chemicals enter the air we breathe as a result of dozens of activities carried out during a typical day at a healthcare facility like processing lab samples, burning fossil fuels etc. We sometimes forget that anesthetic agents are also greenhouse gases (GHGs). Anesthetic agents used today are volatile halogenated ethers and the common carrier gas nitrous oxide known to be aggressive GHGs. With less than 5% of the total delivered halogenated anesthetic being metabolized by the patient, the vast majority of the anesthetic is routinely vented to the atmosphere through the operating room scavenging system. The global warming potential (GWP) of a halogenated anesthetic is up to 2,000 times greater than CO2. Global warming potentials are used to compare the strength of different GHGs to trap heat in the atmosphere relative to that of CO2. Here we discuss about the GWP of anesthetic gases, preventive measures to decrease the global warming effects of anesthetic gases and Xenon, a newer anesthetic gas for the future of anesthesia.

Sedimentary halogens and noble gases within Western Antarctic xenoliths: Implications of extensive volatile recycling to the sub continental lithospheric mantle

NASA Astrophysics Data System (ADS)

Broadley, Michael W.; Ballentine, Chris J.; Chavrit, Déborah; Dallai, Luigi; Burgess, Ray

2016-03-01

Recycling of marine volatiles back into the mantle at subduction zones has a profound, yet poorly constrained impact on the geochemical evolution of the Earth's mantle. Here we present a combined noble gas and halogen study on mantle xenoliths from the Western Antarctic Rift System (WARS) to better understand the flux of subducted volatiles to the sub continental lithospheric mantle (SCLM) and assess the impact this has on mantle chemistry. The xenoliths are extremely enriched in the heavy halogens (Br and I), with I concentrations up to 1 ppm and maximum measured I/Cl ratios (85.2 × 10-3) being ∼2000 times greater than mid ocean ridge basalts (MORB). The Br/Cl and I/Cl ratios of the xenoliths span a range from MORB-like ratios to values similar to marine pore fluids and serpentinites, whilst the 84Kr/36Ar and 130Xe/36Ar ratios range from modern atmosphere to oceanic sediments. This indicates that marine derived volatiles have been incorporated into the SCLM during an episode of subduction related metasomatism. Helium isotopic analysis of the xenoliths show average 3He/4He ratios of 7.5 ± 0.5 RA (where RA is the 3He/4He ratio of air = 1.39 × 10-6), similar to that of MORB. The 3He/4He ratios within the xenoliths are higher than expected for the xenoliths originating from the SCLM which has been extensively modified by the addition of subducted volatiles, indicating that the SCLM beneath the WARS must have seen a secondary alteration from the infiltration and rise of asthenospheric fluids/melts as a consequence of rifting and lithospheric thinning. Noble gases and halogens within these xenoliths have recorded past episodes of volatile interaction within the SCLM and can be used to reconstruct a tectonic history of the WARS. Marine halogen and noble gas signatures within the SCLM xenoliths provide evidence for the introduction and retention of recycled volatiles within the SCLM by subduction related metasomatism, signifying that not all volatiles that survive

Greenhouse Trace Gases in Deadwood

NASA Astrophysics Data System (ADS)

Covey, Kristofer; Bueno de Mesquita, Cliff; Oberle, Brad; Maynard, Dan; Bettigole, Charles; Crowther, Thomas; Duguid, Marlyse; Steven, Blaire; Zanne, Amy; Lapin, Marc; Ashton, Mark; Oliver, Chad; Lee, Xuhui; Bradford, Mark

2016-04-01

Deadwood, long recognized as playing an important role in carbon cycling in forest ecosystems, is more recently drawing attention for its potential role in the cycling of other greenhouse trace gases. We report data from four independent studies measuring internal gas concentrations in deadwood in in three Quercus dominated upland forest systems in the Northeastern and Central United States. Mean methane concentrations in deadwood were 23 times atmospheric levels, indicating a lower bound, mean radial wood surface area flux of ~6 x 10-4 μmol CH4 m-2 s-1. Site, decay class, diameter, and species were all highly significant predictors of methane abundance in deadwood, and log diameter and decay stage interacted as important controls limiting methane concentrations in the smallest and most decayed logs. Nitrous oxide concentrations were negatively correlated with methane and on average ~25% lower than ambient, indicating net consumption of nitrous oxide. These data suggest nonstructural carbohydrates fuel archaeal methanogens and confirm the potential for widespread in situ methanogenesis in both living and deadwood. Applying this understanding to estimate methane emissions from microbial activity in living trees implies a potential global flux of 65.6±12.0 Tg CH4 yr-1, more than 20 times greater than currently considered.

Column amounts of trace gases from ground based FTIR measurements in the late north polar winters 1990 and 1991

NASA Technical Reports Server (NTRS)

Adrian, Gabriele; Blumenstock, Thomas; Fischer, Herbert; Frank, Eckard; Gerhardt, Lothar; Gulde, Thomas; Maucher, Guido; Oelhaf, Hermann; Thomas, Peter; Trieschmann, Olaf

1994-01-01

Two FTIR spectrometers were employed in the late winters 1990 and 1991 in Esrange, North Sweden, and in Ny Aalesund, Spitsbergen to detect zenith column amounts of several trace gases. Time series of column amounts of the trace gases O3, N2O, CH4, HNO3, NO2, CHl, and HF have been derived from the measured spectra. Additionally, some information on the vertical distribution of HCl could be obtained by analyzing the spectral line shapes. The results are interpreted in terms of dynamical and chemical processes.

Halogens in chondritic meteorites and terrestrial accretion

NASA Astrophysics Data System (ADS)

Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

2017-11-01

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

NATIONAL- AND STATE-LEVEL EMISSIONS ESTIMATES OF RADIATIVELY IMPORTANT TRACE GASES (RITGS) FROM ANTHROPOGENIC SOURCES

EPA Science Inventory

The report documents the development of national- and state- level emissions estimates of radiatively important trace gases (RlTGs). Emissions estimates are presented for the principal anthropogenic sources of carbon dioxide (CO2), methane (CH4), chlorofluorocarbons (CFCs), and o...

A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

NASA Technical Reports Server (NTRS)

Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

1998-01-01

Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

Analysis of Process Gases and Trace Contaminants in Membrane-Aerated Gaseous Effluent Streams.

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Lunn, Griffin Michael; Meyer, Caitlin E.

2015-01-01

In membrane-aerated biofilm reactors (MABRs), hollow fibers are used to supply oxygen to the biofilms and bulk fluid. A pressure and concentration gradient between the inner volume of the fibers and the reactor reservoir drives oxygen mass transport across the fibers toward the bulk solution, providing the fiber-adhered biofilm with oxygen. Conversely, bacterial metabolic gases from the bulk liquid, as well as from the biofilm, move opposite to the flow of oxygen, entering the hollow fiber and out of the reactor. Metabolic gases are excellent indicators of biofilm vitality, and can aid in microbial identification. Certain gases can be indicative of system perturbations and control anomalies, or potentially unwanted biological processes occurring within the reactor. In confined environments, such as those found during spaceflight, it is important to understand what compounds are being stripped from the reactor and potentially released into the crew cabin to determine the appropriateness or the requirement for additional mitigation factors. Reactor effluent gas analysis focused on samples provided from Kennedy Space Center's sub-scale MABRs, as well as Johnson Space Center's full-scale MABRs, using infrared spectroscopy and gas chromatography techniques. Process gases, such as carbon dioxide, oxygen, nitrogen, nitrogen dioxide, and nitrous oxide, were quantified to monitor reactor operations. Solid Phase Microextraction (SPME) GC-MS analysis was used to identify trace volatile compounds. Compounds of interest were subsequently quantified. Reactor supply air was examined to establish target compound baseline concentrations. Concentration levels were compared to average ISS concentration values and/or Spacecraft Maximum Allowable Concentration (SMAC) levels where appropriate. Based on a review of to-date results, current trace contaminant control systems (TCCS) currently on board the ISS should be able to handle the added load from bioreactor systems without the need

Development and application of a sampling method for the determination of reactive halogen species in volcanic gas emissions.

PubMed

Rüdiger, Julian; Bobrowski, Nicole; Liotta, Marcello; Hoffmann, Thorsten

2017-10-01

Volcanoes release large amounts of reactive trace gases including sulfur and halogen-containing species into the atmosphere. The knowledge of halogen chemistry in volcanic plumes can deliver information about subsurface processes and is relevant for the understanding of the impact of volcanoes on atmospheric chemistry. In this study, a gas diffusion denuder sampling method using 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated glass tubes for the in situ derivatization of reactive halogen species (RHS) was characterized by a series of laboratory experiments. The coating proved to be applicable to collect selectively gaseous bromine species with oxidation states (OS) of +1 or 0 (such as Br 2 , BrCl, HOBr, BrO, and BrONO 2 ) while being unreactive to HBr (OS -1). The reaction of 1,3,5-TMB with reactive bromine species forms 1-bromo-2,4,6-TMB-other halogens give corresponding derivatives. Solvent elution of the derivatives followed by analysis with GC-MS results in absolute detection limits of a few nanograms for Br 2 , Cl 2 , and I 2 . In 2015, the technique was applied on volcanic gas plumes at Mt. Etna (Italy) measuring reactive bromine mixing ratios between 0.8 and 7.0 ppbv. Total bromine mixing ratios between 4.7 and 27.5 ppbv were derived from alkaline trap samples, simultaneously taken by a Raschig tube and analyzed with IC and ICP-MS. This leads to the first results of the reactive bromine contribution to total bromine in volcanic emissions, spanning over a range between 12% (±1) and 36% (±2). Our finding is in an agreement with previous model studies, which imply values <44% for plume ages <1 min, which is consistent with the assumed plume age at the sampling sites. Graphical abstract Illustration of the measurement procedure for the determination of reactive halogen species in volcanic plumes.

Oxidation of hydrogen halides to elemental halogens

DOEpatents

Rohrmann, Charles A.; Fullam, Harold T.

1985-01-01

A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

A fiber optic sensor with a metal organic framework as a sensing material for trace levels of water in industrial gases.

PubMed

Ohira, Shin-Ichi; Miki, Yusuke; Matsuzaki, Toru; Nakamura, Nao; Sato, Yu-ki; Hirose, Yasuo; Toda, Kei

2015-07-30

Industrial gases such as nitrogen, oxygen, argon, and helium are easily contaminated with water during production, transfer and use, because there is a high volume fraction of water in the atmosphere (approximately 1.2% estimated with the average annual atmospheric temperature and relative humidity). Even trace water (<1 parts per million by volume (ppmv) of H2O, dew point < -76 °C) in the industrial gases can cause quality problems in the process such as production of semiconductors. Therefore, it is important to monitor and to control trace water levels in industrial gases at each supplying step, and especially during their use. In the present study, a fiber optic gas sensor was investigated for monitoring trace water levels in industrial gases. The sensor consists of a film containing a metal organic framework (MOF). MOFs are made of metals coordinated to organic ligands, and have mesoscale pores that adsorb gas molecules. When the MOF, copper benzene-1,3,5-tricarboxylate (Cu-BTC), was used as a sensing material, we investigated the color of Cu-BTC with water adsorption changed both in depth and tone. Cu-BTC crystals appeared deep blue in dry gases, and then changed to light blue in wet gases. An optical gas sensor with the Cu-BTC film was developed using a light emitting diode as the light source and a photodiode as the light intensity detector. The sensor showed a reversible response to trace water, did not require heating to remove the adsorbed water molecules. The sample gas flow rate did not affect the sensitivity. The obtained limit of detection was 40 parts per billion by volume (ppbv). The response time for sample gas containing 2.5 ppmvH2O was 23 s. The standard deviation obtained for daily analysis of 1.0 ppmvH2O standard gas over 20 days was 9%. Furthermore, the type of industrial gas did not affect the sensitivity. These properties mean the sensor will be applicable to trace water detection in various industrial gases. Copyright © 2015 Elsevier B

Global emissions of trace gases, particulate matter, and hazardous air pollutants from open burning of domestic waste.

PubMed

Wiedinmyer, Christine; Yokelson, Robert J; Gullett, Brian K

2014-08-19

The open burning of waste, whether at individual residences, businesses, or dump sites, is a large source of air pollutants. These emissions, however, are not included in many current emission inventories used for chemistry and climate modeling applications. This paper presents the first comprehensive and consistent estimates of the global emissions of greenhouse gases, particulate matter, reactive trace gases, and toxic compounds from open waste burning. Global emissions of CO2 from open waste burning are relatively small compared to total anthropogenic CO2; however, regional CO2 emissions, particularly in many developing countries in Asia and Africa, are substantial. Further, emissions of reactive trace gases and particulate matter from open waste burning are more significant on regional scales. For example, the emissions of PM10 from open domestic waste burning in China is equivalent to 22% of China's total reported anthropogenic PM10 emissions. The results of the emissions model presented here suggest that emissions of many air pollutants are significantly underestimated in current inventories because open waste burning is not included, consistent with studies that compare model results with available observations.

Climate-chemical interactions and greenhouse effects of trace gases

NASA Technical Reports Server (NTRS)

Shi, Guang-Yu; Fan, Xiao-Biao

1994-01-01

A completely coupled one-dimensional radiative-convective (RC) and photochemical-diffusion (PC) model has been developed recently and used to study the climate-chemical interactions. The importance of radiative-chemical interactions within the troposphere and stratosphere has been examined in some detail. We find that increases of radiatively and/or chemically active trace gases such as CO2, CH4 and N2O have both the direct effects and the indirect effects on climate change by changing the atmospheric O3 profile through their interaction with chemical processes in the atmosphere. It is also found that the climatic effect of ozone depends strongly on its vertical distribution throughout the troposphere and stratosphere, as well on its column amount in the atmosphere.

Potential for the use of reconstructed IASI radiances in the detection of atmospheric trace gases

NASA Astrophysics Data System (ADS)

Atkinson, N. C.; Hilton, F. I.; Illingworth, S. M.; Eyre, J. R.; Hultberg, T.

2010-02-01

Principal component (PC) analysis has received considerable attention as a technique for the extraction of meteorological signals from hyperspectral infra-red sounders such as the Infrared Atmospheric Sounding Interferometer (IASI) and the Atmospheric Infrared Sounder (AIRS). In addition to achieving substantial bit-volume reductions for dissemination purposes, the technique can also be used to generate reconstructed radiances in which random instrument noise has been suppressed. To date, most studies have been in the context of Numerical Weather Prediction (NWP). This study examines the potential of PC analysis for chemistry applications. A major concern in the use of PC analysis for chemistry has been that the spectral features associated with trace gases may not be well represented in the reconstructed spectra, either due to deficiencies in the training set or due to the limited number of PC scores used in the radiance reconstruction. In this paper we show examples of reconstructed IASI radiances for several trace gases: ammonia, sulphur dioxide, methane and carbon monoxide. It is shown that care must be taken in the selection of spectra for the initial training set: an iterative technique, in which outlier spectra are added to a base training set, gives the best results. For the four trace gases examined, the chemical signatures are retained in the reconstructed radiances, whilst achieving a substantial reduction in instrument noise. A new regional re-transmission service for IASI is scheduled to start in 2010, as part of the EUMETSAT Advanced Retransmission Service (EARS). For this EARS-IASI service it is intended to include PC scores as part of the data stream. The paper describes the generation of the reference eigenvectors for this new service.

Halogens in normal- and enriched-basalts from Central Indian Ridge (18-20°S): Testing the E-MORB subduction origin hypothesis

NASA Astrophysics Data System (ADS)

Ruzie, L.; Burgess, R.; Hilton, D. R.; Ballentine, C. J.

2012-12-01

Basalts emitted along oceanic ridges have often been subdivided into two categories: the Normal-MORB and the Enriched-MORB, anomalously enriched in highly incompatible elements. Donnelly et al. (2004) proposed that the formation of enriched sources is related to two stages of melting. The first one occurs in subduction zones where the mantle wedge is enriched by the addition of low-degree melts of subducted slab. The second stage of melting occurs beneath ocean ridges. Because of their incompatibility, relatively high concentrations and distinct elemental compositions in surface reservoirs, the heavy halogens (Cl, Br, I) are good tracers to detect the slab contribution in E-MORB sources. However, the halogen systematics in mantle reservoirs remains poorly constrained mainly because of their very low abundance in materials of interest. An innovative halogen analytical technique, developed at the University of Manchester, involving neutron irradiation of samples to convert halogens to noble gases provides detection limits unmatched by any other technique studies [Johnson et al. 2000]. For the first time Cl, Br and I can now be determined in appropriate samples. We focus on the content of halogens in the glassy margins of basalts erupted along the CIR from 18-20°S and the off-axis Gasitao Ridge. Our set of samples contains both N- and E-MORB and is fully described in terms of major and trace elements, as well as 3He/4He ratios and water concentrations [Murton et al., 2005; Nauret et al., 2006; Füri et al., 2011; Barry et al., in prep.]. The halogen concentration range is between 10 and 140 ppm for Cl, 30 and 500 ppb for Br and 0.8 and 10 ppb for I. The higher concentrations are found in E-MORB samples from the northern part of ridge axis. Comparing our data with previous halogen studies, our sample suites fall within the range of N-MORB from East Pacific Ridge (EPR) and Mid-Atlantic Ridge (MAR) [Jambon et al. 1995; Deruelle et al. 1992] and in the lower range of E

40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1) An...

High sensitivity detection of trace gases at atmospheric pressure using tunable diode lasers

NASA Technical Reports Server (NTRS)

Reid, J.; Sinclair, R. L.; Grant, W. B.; Menzies, R. T.

1985-01-01

A detailed study of the detection of trace gases at atmospheric pressure using tunable diode lasers is described. The influence of multipass cells, retroreflectors and topographical targets is examined. The minimum detectable infrared absorption ranges from 0.1 percent for a pathlength of 1.2 km to 0.01 percent over short pathlengths. The factors which limit this sensitivity are discussed, and the techniques are illustrated by monitoring atmospehric CO2 and CH4.

Health Hazard Evaluation Report HETA 84-145-1604, Porter Memorial Hospital, Valparaiso, Indiana. [Anesthetic gases and ethylene oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Behrens, V.; Burroughs, G.E.; Crandall, M.

1985-07-01

Environmental and breathing-zone samples were analyzed for nitrous oxide, halogenated anesthetic gases, and ethylene-oxide at Porter Memorial Hospital, Valparaiso, Indiana in April, 1984. The evaluation was requested by the Indiana Occupational Safety and Health Administration to investigate the exposure of operating room personnel to anesthetic gases and central supply employees to ethylene-oxide. The authors conclude that some of the operating room personnel are overexposed to halogenated anesthetic gases and nitrous-oxide. Recommendations include performing better maintenance of the anesthesia equipment, improving the work practices of the anesthesiologists, and periodically checking the ethylene-oxide sterilizer system for leaks.

Potential for the use of reconstructed IASI radiances in the detection of atmospheric trace gases

NASA Astrophysics Data System (ADS)

Atkinson, N. C.; Hilton, F. I.; Illingworth, S. M.; Eyre, J. R.; Hultberg, T.

2010-07-01

Principal component (PC) analysis has received considerable attention as a technique for the extraction of meteorological signals from hyperspectral infra-red sounders such as the Infrared Atmospheric Sounding Interferometer (IASI) and the Atmospheric Infrared Sounder (AIRS). In addition to achieving substantial bit-volume reductions for dissemination purposes, the technique can also be used to generate reconstructed radiances in which random instrument noise has been reduced. Studies on PC analysis of hyperspectral infrared sounder data have been undertaken in the context of numerical weather prediction, instrument monitoring and geophysical variable retrieval, as well as data compression. This study examines the potential of PC analysis for chemistry applications. A major concern in the use of PC analysis for chemistry is that the spectral features associated with trace gases may not be well represented in the reconstructed spectra, either due to deficiencies in the training set or due to the limited number of PC scores used in the radiance reconstruction. In this paper we show examples of reconstructed IASI radiances for several trace gases: ammonia, sulphur dioxide, methane and carbon monoxide. It is shown that care must be taken in the selection of spectra for the initial training set: an iterative technique, in which outlier spectra are added to a base training set, gives the best results. For the four trace gases examined, key features of the chemical signatures are retained in the reconstructed radiances, whilst achieving a substantial reduction in instrument noise. A new regional re-transmission service for IASI is scheduled to start in 2010, as part of the EUMETSAT Advanced Retransmission Service (EARS). For this EARS-IASI service it is intended to include PC scores as part of the data stream. The paper describes the generation of the reference eigenvectors for this new service.

Interannual variability of trace gases in the subtropical winter stratosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gray, L.J.; Russell, J.M. III

1999-04-01

Measurements of water vapor and methane from the Halogen Occultation Experiment instrument on board the Upper Atmosphere Research Satellite are used to study the interannual variability of trace gas distributions in the atmosphere. Particular attention is paid to the mechanisms influencing trace gas distributions in the subtropics. The study highlights the quasi-biennial oscillation (QBO) dependence of subtropical tracer distributions more clearly than in previous studies. There is a strong correlation between the equatorial wind QBO and the slope of the tracer isolines in the Northern Hemisphere subtropics, with steeper subtropical isoline slopes in the easterly phase compared with the westerlymore » phase. This is particularly so in the lower stratosphere. Two possible mechanisms for the QBO signal in subtropical isoline slopes are identified: advection by the mean circulation and isentropic mixing. A comparison between the QBO signal in the slope of the tracer isolines and the isentropic tracer gradients is proposed as a method of determining which process is dominant. The authors suggest that the behavior of these two data diagnostics provides a stringent constraint on computer models of the atmosphere. On the basis of these diagnostics three height regions of the subtropical atmosphere are identified. (1) Below 450--500 K isentropic mixing associated with tropospheric disturbances penetrating the lower stratosphere is dominant. (2) In the region 500--750 K the data suggest that advection by the mean meridional circulation is important and that the role of isentropic mixing by eddies is relatively small. (3) Above 750 K isentropic mixing becomes increasingly important with height, and both advection and mixing are influential in determining the subtropical tracer distributions.« less

What can surface measurements of long-lived trace gases tell us about interannual variability in UTLS transport?

NASA Astrophysics Data System (ADS)

Ray, E. A.; Daniel, J. S.; Montzka, S. A.; Portmann, R. W.; Yu, P.; Rosenlof, K. H.; Moore, F. L.

2017-12-01

We use surface measurements of a number of long-lived trace gases, including CFC-11, CFC-12 and N2O, and a 3-box model to estimate the interannual variability of bulk stratospheric transport characteristics. Coherent features among the different surface measurements suggest that there have been periods over the last two decades with significant variability in the amount of stratospheric loss transported downward to the troposphere both globally and between the NH and SH. This is especially apparent around the year 2000 and in the recent period since 2013 when surface measurements suggest an overall slowdown of the transport of stratospheric air to the troposphere as well as a shift towards a relatively stronger stratospheric circulation in the SH compared to the NH. We compare these results to stratospheric satellite measurements, residual circulation estimates and global model simulations to check for consistency. The implications of not accounting for interannual variability in stratospheric loss transported to the surface in emission estimates of long-lived trace gases can be significant, including for those gases monitored by the Montreal Protocol and/or of climatic importance.

Development of Optical Parametric Amplifier for Lidar Measurements of Trace Gases on Earth and Mars

NASA Technical Reports Server (NTRS)

Numata, Kenji; Riris, Haris; Li, Steve; Wu, Stewart; Kawa, Stephen R.; Krainak, Michael; Abshire, James

2011-01-01

Trace gases in planetary atmospheres offer important clues as to the origins of the planet's hydrology, geology. atmosphere. and potential for biology. Wc report on the development effort of a nanosecond-pulsed optical parametric amplifier (OPA) for remote trace gas measurements for Mars and Earth. The OP A output light is single frequency with high spectral purity and is widely tunable both at 1600 nm and 3300 nm with an optical-optical conversion efficiency of approximately 40%. We demonstrated open-path atmospheric measurements ofCH4 (3291 nm and 1651 nm). CO2 (1573 nm), H20 (1652 nm) with this laser source.

Measurements of Trace Gases Using a Tunable Diode Laser

NASA Technical Reports Server (NTRS)

Jost, Hans-Juerg

2005-01-01

This report is the final report for "Measurements of Trace Gases Using a Tunable Diode Laser." The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally, the important publications are attached. The Cooperative Agreement made possible a research effort to produce high- precision and high-accuracy in-situ measurements of carbon monoxide, methane and nitrous oxide on the WB-57 during the CRYSTAL-FACE and pre-AVE field campaigns and to analyze these measurements. These measurements of CO and CH4 were of utmost importance to studies of the radiative effects of clouds. Some important results of the CRYSTAL-FACE program were contained in two scientific papers (attached). This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.

40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2012 CFR

2012-07-01

... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according to...

40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2014 CFR

2014-07-01

... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according to...

40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2010 CFR

2010-07-01

... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according to...

40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2013 CFR

2013-07-01

... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according to...

40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

Code of Federal Regulations, 2011 CFR

2011-07-01

... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according to...

Global Observations of Inorganic Gases in the Remote Atmosphere - First Observations from the Atmospheric Tomography Mission (ATom)

NASA Astrophysics Data System (ADS)

Veres, P. R.; Neuman, J. A.

2017-12-01

The Atmospheric Tomography Mission (ATom) is a NASA field program that investigates the impact of human emissions on air quality and climate in remote regions of the atmosphere. NASA DC-8 flights during the ATom sampled the atmosphere over the Pacific and Atlantic Oceans, up to 12 km altitude and nearly from pole to pole. New observations of key species (e.g. N2O5, reactive halogens, nitrous acid) in these regions are provided during the third deployment of the NASA DC-8 research aircraft (October, 2017) by the NOAA iodide ion time-of-flight chemical ionization mass spectrometer (iCIMS). In this study, we will present the first observations of inorganic gas-phase species using iCIMS from the ATom 3 deployment. Laboratory results detailing the instrument performance including inlet response times, background characterization and sensitivity will be presented. We will show vertical profiles of newly measured trace gases derived from in-situ observations, and discuss the potential impact on the NOx, NOy and reactive halogen budgets.

Development and application of a sampling method for the determination of reactive halogen species in volcanic gas emissions

NASA Astrophysics Data System (ADS)

Rüdiger, Julian; Bobrowski, Nicole; Liotta, Marcello; Hoffmann, Thorsten

2017-04-01

Volcanoes are a potential large source of several reactive atmospheric trace gases including sulfur and halogen containing species. Besides the importance for atmospheric chemistry, the detailed knowledge of halogen chemistry in volcanic plumes can help to get insights into subsurface processes. In this study a gas diffusion denuder sampling method, using a 1,3,5-trimethoxybenzene (1,3,5-TMB) coating for the derivatization of reactive halogen species (RHS), was characterized by dilution chamber experiments. The coating proved to be suitable to collect selectively gaseous bromine species with oxidation states (OS) of +1 or 0 (such as Br2, BrCl, BrO(H) and BrONO2), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with reactive bromine species gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography mass spectrometry gives detection limits of 10 ng or less for Br2, Cl2, and I2. In 2015 the method was applied on volcanic gas plumes at Mt. Etna (Italy) giving reactive bromine mixing ratios from 0.8 ppbv to 7.0 ppbv. Total bromine mixing ratios of 4.7 ppbv to 27.5 ppbv were obtained by simultaneous alkaline trap sampling (by a Raschig-tube) followed by analysis with ion chromatography and inductively coupled plasma mass spectrometry. This leads to the first results of in-situ measured reactive bromine to total bromine ratios, spanning a range between 12±1 % and 36±2 %. Our finding is in an agreement with previous model studies, which imply values < 44 % for plume ages < 1 minute, which is consistent with the assumed plume age at the sampling sites.

Noble Gases Trace Earth's Subducted Water Flux

NASA Astrophysics Data System (ADS)

Smye, A.; Jackson, C.; Konrad-Schmolke, M.; Parman, S. W.; Ballentine, C. J.

2016-12-01

Volatile elements are transported from Earth's surface reservoirs back into the mantle during subduction of oceanic lithosphere [e.g. 1]. Here, we investigate the degree to which the fate of slab-bound noble gases and water are linked through the subduction process. Both water and noble gases are soluble in ring-structured minerals, such as amphibole, that are common constituents of subducted oceanic lithosphere. Heating and burial during subduction liberates noble gases and water from minerals through a combination of diffusion and dissolution. Combining a kinetic model, parameterized for noble gas fractionation in amphibole [2], with thermodynamic phase equilibria calculations, we quantify the effect of subduction dehydration on the elemental composition of slab-bound noble gases. Results show that post-arc slab water and noble gas fluxes are highly correlated. Hot subduction zones, which likely dominate over geologic history, efficiently remove noble gases and water from the down-going slab; furthermore, kinetic fractionation of noble gases is predicted to occur beneath the forearc. Conversely, hydrated portions of slab mantle in cold subduction zones transport noble gases and water to depths exceeding 200 km. Preservation of seawater-like abundances of Ar, Kr and Xe in the convecting mantle [1] implies that recycling of noble gases and water occurred during cold subduction and that the subduction efficiency of these volatile elements has increased over geological time, driven by secular cooling of the mantle. [1] Holland, G. and Ballentine, C. (2006). Nature 441, 186-191. [2] Jackson et al. (2013). Nat.Geosci. 6, 562-565.

A versatile, refrigerant- and cryogen-free cryofocusing-thermodesorption unit for preconcentration of traces gases in air

NASA Astrophysics Data System (ADS)

Obersteiner, Florian; Bönisch, Harald; Keber, Timo; O'Doherty, Simon; Engel, Andreas

2016-10-01

We present a compact and versatile cryofocusing-thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. -80 °C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. +200 °C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography - mass spectrometry (GC-MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately -80 to +150 °C and a substance mixing ratio range of less than 1 ppt (pmol mol-1) to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC-MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer).

Cosmic-Ray Reaction and Greenhouse Effect of Halogenated Molecules: Culprits for Atmospheric Ozone Depletion and Global Climate Change

NASA Astrophysics Data System (ADS)

Lu, Q.-B.

2013-07-01

This study is focused on the effects of cosmic rays (solar activity) and halogen-containing molecules (mainly chlorofluorocarbons — CFCs) on atmospheric ozone depletion and global climate change. Brief reviews are first given on the cosmic-ray-driven electron-induced-reaction (CRE) theory for O3 depletion and the warming theory of halogenated molecules for climate change. Then natural and anthropogenic contributions to these phenomena are examined in detail and separated well through in-depth statistical analyses of comprehensive measured datasets of quantities, including cosmic rays (CRs), total solar irradiance, sunspot number, halogenated gases (CFCs, CCl4 and HCFCs), CO2, total O3, lower stratospheric temperatures and global surface temperatures. For O3 depletion, it is shown that an analytical equation derived from the CRE theory reproduces well 11-year cyclic variations of both polar O3 loss and stratospheric cooling, and new statistical analyses of the CRE equation with observed data of total O3 and stratospheric temperature give high linear correlation coefficients ≥ 0.92. After the removal of the CR effect, a pronounced recovery by 20 25 % of the Antarctic O3 hole is found, while no recovery of O3 loss in mid-latitudes has been observed. These results show both the correctness and dominance of the CRE mechanism and the success of the Montreal Protocol. For global climate change, in-depth analyses of the observed data clearly show that the solar effect and human-made halogenated gases played the dominant role in Earth's climate change prior to and after 1970, respectively. Remarkably, a statistical analysis gives a nearly zero correlation coefficient (R = -0.05) between corrected global surface temperature data by removing the solar effect and CO2 concentration during 1850-1970. In striking contrast, a nearly perfect linear correlation with coefficients as high as 0.96-0.97 is found between corrected or uncorrected global surface temperature and total

Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

NASA Astrophysics Data System (ADS)

Williams, M. J.; Kendrick, M. A.; Rubatto, D.

2017-12-01

A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens

Emission rates of sulfur dioxide, trace gases and metals from Mount Erebus, Antartica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyle, P.R.; Meeker, K.; Finnegan, D.

1990-11-01

SO{sub 2} emission rates have been measured annually since 1983 at Mount Erebus, Antarctica by correlation spectrometer (COSPEC V). Following a 4 month period of sustained strombolian activity in late 1984, SO{sub 2} emissions declined from 230 Mg/day in 1983 to 25 Mg/day and then slowly increased from 16 Mg/day in 1985 to 51 Mg/day in 1987. Nine sets of filter packs containing partcle and {sup 7}LiOH treated filters were collected in the plume in 1986 and analyzed by neutron activation. Using the COSPEC data and measured element/S ratios on the filters, emission rates have been determined for trace gasesmore » and metals. The authors infer HCl and HF emissions in 1983 to be about 1200 and 500 Mg/day, respectively. Mt Erebus has therefore been an important source of halogens to the Anarctic atmosphere and could be responsible for excess Cl found in Central Antarctica snow.« less

Method and apparatus for detecting and measuring trace impurities in flowing gases

DOEpatents

Taylor, Gene W.; Dowdy, Edward J.

1979-01-01

Trace impurities in flowing gases may be detected and measured by a dynamic atomic molecular emission spectrograph utilizing as its energy source the energy transfer reactions of metastable species, atomic or molecular, with the impurities in the flowing gas. An electronically metastable species which maintains a stable afterglow is formed and mixed with the flowing gas in a region downstream from and separate from the region in which the metastable species is formed. Impurity levels are determined quantitatively by the measurement of line and/or band intensity as a function of concentration employing emission spectroscopic techniques.

Stratospheric measurements of ozone-depleting substances and greenhouse gases using AirCores

NASA Astrophysics Data System (ADS)

Laube, Johannes; Leedham Elvidge, Emma; Kaiser, Jan; Sturges, Bill; Heikkinen, Pauli; Laurila, Tuomas; Hatakka, Juha; Kivi, Rigel; Chen, Huilin; Fraser, Paul; van der Veen, Carina; Röckmann, Thomas

2017-04-01

Retrieving air samples from the stratosphere has previously required aircraft or large balloons, both of which are expensive to operate. The novel "AirCore" technique (Karion et al., 2010) enables stratospheric sampling using weather balloons, which is much more cost effective. AirCores are long (up to 200 m) stainless steel tubes which are placed as a payload on a small balloon, can ascend to over 30 km and fill upon descent, collecting a vertical profile of the atmosphere. Retrieved volumes are much smaller though, which presents a challenge for trace gas analysis. To date, only the more abundant trace gases such as carnon dioxide (CO2) and methane (CH4) have been quantified in AirCores. Halogenated trace gases are also important greenhouse gases and many also deplete stratospheric ozone. Their concentrations are however much lower i.e. typically in the part per trillion (ppt) molar range. We here present the first stratospheric measurements of halocarbons in AirCores obtained using UEA's highly sensitive (detection limits of 0.01-0.1 ppt in 10 ml of air) gas chromatography mass spectrometry system. The analysed air originates from a Stratospheric Air Sub-sampler (Mrozek et al., 2016) which collects AirCore segments after the non-destructive CO2 and CH4 analysis. Successfully measured species include CFC-11, CFC-12, CFC-113, CFC-115, H-1211, H-1301, HCFC-22, HCFC-141b, HCFC-142b, HCFC-133a, and sulphur hexafluoride (SF6). We compare the observed mixing ratios and precisions with data obtained from samples collected during various high-altitude aircraft campaigns between 2009 and 2016 as well as with southern hemisphere tropospheric long-term trends. As part of the ERC-funded EXC3ITE (EXploring stratospheric Composition, Chemistry and Circulation with Innovative Techniques) project more than 40 AirCore flights are planned in the next 3 years with an expanded range of up to 30 gases in order to explore seasonal and interannual variability in the stratosphere

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

USGS Publications Warehouse

Plummer, Niel; Sibrell, Philip L.; Casile, Gerolamo C.; Busenberg, Eurybiades; Hunt, Andrew G.; Schlosser, Peter

2013-01-01

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3H/3He and SF6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg−1), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3H/3He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg

Noble gases and halogens in Graves Nunataks 06129: The complex thermal history of a felsic asteroid crust

NASA Astrophysics Data System (ADS)

Claydon, Jennifer L.; Crowther, Sarah A.; Fernandes, Vera A.; Gilmour, Jamie D.

2015-06-01

The meteorite Graves Nunataks 06128/06129 is a rare example of felsic asteroidal crust. Knowledge of its history can help shed light on the evolution processes of planetesimals. The noble gases can be used to constrain both the chronology of meteorites and the processes that result in movements of volatile elements on asteroidal bodies. We have examined the I-Xe and Ar-Ar systems of the plagioclase-rich achondrite, Graves Nunataks 06129 by high-resolution laser step-heating of irradiated samples. Iodine and 129Xe∗ are both present but are released at different temperatures and do not show a correlation, therefore the I-Xe system in GRA 06129 has no chronological significance. We propose that radiogenic 129Xe∗ was lost from primary phases and parentless 129Xe∗ was later introduced into the rock by interaction with a fluid sourced from a reservoir that evolved with a high I/Xe ratio. This could have been the same halogen-rich fluid that induced the conversion of merrillite and pyroxene into chlorapatite. Inherited 40Ar (i.e. not generated by in situ decay of 40K) is also present in one of three fragments studied here and may have been introduced at the same time as parentless 129Xe∗.

Sulfur and halogen gases at Masaya Caldera Complex, Nicaragua: Total flux and variations with time

NASA Astrophysics Data System (ADS)

Stoiber, Richard E.; Williams, Stanley N.; Huebert, Barry J.

1986-11-01

Santiago Crater, of Masaya Caldera Complex near Managua, Nicaragua, entered a phase of intense magmatic degassing in late 1979. The flux of SO2 increased rapidly from a previous average of 380 t d-1 to approximately 1200 t d-1 in February 1980. We report on results of a study of the gas flux and geochemistry conducted as part of a broader interdisciplinary study of the volcano and its impact on the adjacent environment. Masaya is an unusual volcano because of its low shield like form, consistent tholeiitic basaltic composition, frequent activity, and especially because of the approximately 25 year cycle of major non-eruptive degassing crises. We have used a combination of techniques involving remote sensing (using a correlation spectrometer (COSPEC)) of the flux of SO2 and direct filter sampling of the ratios of the sulfur and halogen gases and aerosols to quantify the flux of all of these species. The three-stage filters successively trap aerosols, halogen acid gases, and sulfur dioxide and are analyzed by ion chromatography. We have used the ratios of various species, with the COSPEC measurements of the flux of SO2, to calculate that the average flux of SO2 is 1275 t d-1, HCl is 830 t d-1, HF is about 16 t d-1, and HBr is at most 1 t d-1. H2S and SO4 = are only minor sulfur species. The flux of SO2 and HCl represents the largest reported noneruptive sustained volcanic release of these species in the world. Masaya contributed 7% of the total SO2 estimated to have been released by volcanoes worldwide in 1981. The flux of SO2 has declined by about 9% each year since 1979 and can be modeled as a first-order kinetic rate law with a decay constant of approximately 0.04 yr-1. Approximately 2.2 × 106 tons of SO2 has been released between September 1979 and September 1985. The ratio S/Cl has declined more rapidly than the flux of SO2, reflecting the greater solubility of HCl than SO2 in the magma. The SO2 flux at Santiago varies more widely within a single day than

Environmental factors controlling transient and seasonal changes of trace gases within shallow vadose zone

NASA Astrophysics Data System (ADS)

Pla, Concepcion; Galiana-Merino, Juan Jose; Cuezva, Soledad; Fernandez-Cortes, Angel; Garcia-Anton, Elena; Cuevas, Jaime; Cañaveras, Juan Carlos; Sanchez-Moral, Sergio; Benavente, David

2014-05-01

Shallow vadose environments below soil, mainly caves, show significant seasonal and even daily variations in gas composition of ground air, which involves the exchange of large amounts of gases, e.g. greenhouse gases (GHGs) as CO2 or CH4, with the lower troposphere. To understand better the role of caves as a sink or depot of GHGs, geochemical tracing of air (atmosphere, soil and ground air) was performed at Rull cave (southeast Spain) by monitoring CH4, CO2 and the stable carbon isotopic delta13C[CO2] using cavity ring-down spectroscopy (CRDS). A comprehensive microclimatic monitoring of exterior and cave atmosphere was simultaneously conducted to GHGs-tracking, including factors as temperature, barometric pressure, relative humidity and concentration of CO2 and 222Rn. The analysis of the measured data allows understanding outgassing and isolation processes taking place in the karst cavity. Annual patterns of gases behaviour can be distinguished, depending on the prevailing relationship between outer atmosphere, indoor atmosphere and soil system. Cave air temperature fluctuates around 15.7 ºC and relative humidity remains higher than 96% the whole annual cycle. The mean concentration of 222Rn is 1584 Bq m-3 while CO2 remains 1921 ppm. When external temperature is higher of indoor temperature (April-October), the highest levels of both trace gases are reached, while levels drop to its lowest values in the coldest months. Preliminary results obtained show an annual variation in concentration of CO2 inside the cave between 3300 ppm and 900 ppm, whereas corresponding isotopic signal delta13CO2 varies between -24‰ and -21‰. The results have been studied by Keeling model that approximates the isotopic signal of the source contribution in a resulting air mix. The values registered inside the cave were represented joined to results for exterior air (average values round 410 ppm of CO2 and -9 ‰ for delta13C). Value obtained is -27‰ pointing to a high influence of

The airborne mass spectrometer AIMS - Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

NASA Astrophysics Data System (ADS)

Jurkat, Tina; Kaufmann, Stefan; Voigt, Christiane; Schäuble, Dominik; Jeßberger, Philipp; Ziereis, Helmut

2016-04-01

Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulfur compounds. The Atmospheric chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using SF5- reagent ions for the simultaneous measurement of trace gas concentrations of HCl, HNO3 and SO2 in the pptv to ppmv (10-12 to 10-6 mol mol-1) range with in-flight and online calibration called AIMS-TG (Atmospheric chemical Ionization Mass Spectrometer for measurements of trace gases). Part 1 of this paper (Kaufmann et al., 2016) reports on the UTLS water vapor measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed for generation of reagent ions that selectively react with HCl, HNO3, SO2 and HONO. HNO3 and HCl are routinely calibrated in-flight using permeation devices; SO2 is continuously calibrated during flight adding an isotopically labeled 34SO2 standard. In addition, we report on trace gas measurements of HONO, which is sensitive to the reaction with SF5-. The detection limit for the various trace gases is in the low 10 pptv range at a 1 s time resolution with an overall uncertainty of the measurement of the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO (High Altitude LOng range research aircraft). As an example, measurements conducted during the TACTS/ESMVal (Transport and Composition of the LMS/UT and Earth System Model Validation) mission with

The Atmosphere of Crystal Cave: Understanding Sources and Sinks of Trace Gases

NASA Astrophysics Data System (ADS)

Jarnot, A. W.; Hughes, S.; Blake, D. R.

2016-12-01

The atmospheric chemistry of cave systems has not been previously studied in depth; however, cave systems are prime locations to study potential sources and sinks for trace gas pollutants. Relatively constant temperatures, humidity, minimal air flow, and lack of sunlight create a stable environment that allows for biogeochemical processes to go on uninterrupted for extended periods of time. Carbonyl sulfide (OCS) is one of the main contributors to air pollution globally, but many OCS sinks are not fully understood. A preliminary analysis of cave air from Crystal Cave in Sequoia National Park yielded OCS concentrations of 35.2 ± 0.7 pptv, approximately 16 times lower than the average concentration of 568 ± 8 pptv measured outside of the cave. In addition, the concentrations of several other trace gases such as alpha-pinene and methyl bromide were found to be abnormally low (10.5 ± 0.3 pptv inside and 387 ± 8 pptv for alpha-pinene, and 387 ± 8 pptv inside and 11.1 ± 0.4 pptv outside for methyl bromide). The cave air was found to be well-mixed as the concentrations of long lived halocarbons such as CFC-12 were similar inside and outside of the cave (545 ± 5 pptv and 538 ± 4 pptv, respectively). This indicates that there may be one or more factors causing the cave to act a sink for several trace gas species. Further sampling and analysis of the atmosphere in the cave is required to draw any concrete conclusions about the unique environment presented here. The information gathered will help elucidate mechanisms for trace gas degradation, which could yield information about global trace gas budgets and their effect on global air quality.

Trace Gases and Aerosols Simulated Over the Indian Domain: Evaluation of the Model Wrf-Chem

NASA Astrophysics Data System (ADS)

Michael, M.; Yadav, A.; Tripathi, S. N.; Venkataraman, C.; Kanawade, V. P.

2012-12-01

As the anthropogenic emissions from the Asian countries contribute substantially to the global aerosol loading, the study of the distribution of trace gases and aerosols over this region has received increasing attention in recent years. In the present work, the aerosol properties over the Indian domain during the pre-monsoon season has been addressed. The "online" meteorological and chemical transport Weather Research and Forecasting-Chemistry (WRF-Chem) model has been implemented over Indian subcontinent for three consecutive summers in 2008, 2009 and 2010.The initial and boundary conditions are obtained from NCAR reanalysis data. The global emission inventories (REanalysis of the TROpospheric chemical composition (RETRO) and Emissions Database for Global Atmospheric Research (EDGAR)) have been used and are projected for the period of study using the method provided in Ohara et al. (2007). The emission rates of sulfur dioxide, black carbon, organic carbon and PM2.5 available in the global inventory are replaced with the high resolution emission inventory developed over India for the present study. The model simulates meteorological parameters, trace gases and particulate matter. Simulated mixing ratios of trace gases (Ozone, carbon monoxide, nitrogen oxides, and SO2) are compared with ground based as well as satellite observations over India with specific focus on Indo-Gangetic Plain. Simulated aerosol optical depth are in good agreement with those observed by Aerosol Robotic Network (AERONET). The vertical profiles of extinction coefficient have been compared with the Micro Pulse Lidar Network (MPLnet) data. The simulated mass concentration of BC shows very good agreement with those observed at a few ground stations. The vertical profiles of BC have also been compared with aircraft observations carried out during summer of 2008 and 2009, resulting in good agreement. This study shows that WRF-Chem model captures many important features of the observations and

WET EFFLUENT PARALLEL PLATE DIFFUSION DENUDER COUPLED CAPILLARY ION CHROMATOGRAPH FOR THE DETERMINATION OF ATMOSPHERIC TRACE GASES. (R825344)

EPA Science Inventory

We describe an inexpensive, compact parallel plate diffusion denuder coupled capillary IC system for the determination of soluble ionogenic atmospheric trace gases. The active sampling area (0.6×10 cm) of the denuder is formed in a novel manner by thermally bonding silica ge...

Phase Partitioning of Soluble Trace Gases with Size-Resolved Aerosols during the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) Campaign

NASA Astrophysics Data System (ADS)

Young, A.; Keene, W. C.; Pszenny, A.; Sander, R.; Maben, J. R.; Warrick-Wriston, C.; Bearekman, R.

2011-12-01

During February and March 2011, size-resolved and bulk aerosol were sampled at 22 m above the surface over nominal 12-hour (daytime and nighttime) intervals from the Boulder Atmospheric Observatory tower (40.05 N, 105.01 W, 1584-m elevation). Samples were analyzed for major organic and inorganic ionic constituents by high performance ion chromatography (IC). Soluble trace gases (HCl, HNO3, NH3, HCOOH, and CH3COOH) were sampled in parallel over 2-hour intervals with tandem mist chambers and analyzed on site by IC. NH4+, NO3-, and SO42- were the major ionic components of aerosols (median values of 57.7, 34.5, and 7.3 nmol m-3 at STP, respectively, N = 45) with 86%, 82%, and 82%, respectively, associated with sub-μm size fractions. Cl- and Na+ were present at significant concentrations (median values of 6.8 and 6.6 nmol m-3, respectively) but were associated primarily with super-μm size fractions (75% and 78%, respectively). Median values (and ranges) for HCl, HNO3, and NH3 were 21 (<20-1257), 120 (<45-1638), and 5259 (<1432-48,583) pptv, respectively. Liquid water contents of size-resolved aerosols and activity coefficients for major ionic constituents were calculated with the Extended Aerosol Inorganic Model II and IV (E-AIM) based on the measured aerosol composition, RH, temperature, and pressure. Size-resolved aerosol pHs were inferred from the measured phase partitioning of HCl, HNO3, and NH3. Major controls of phase partitioning and associated chemical dynamics will be presented.

Application of ion chemistry and the SIFT technique to the quantitative analysis of trace gases in air and on breath

NASA Astrophysics Data System (ADS)

Smith, David; Španěl, Patrik

Our major objective in this paper is to describe a new method we have developed for the analysis of trace gases at partial pressures down to the ppb level in atmospheric air, with special emphasis on the detection and quantification of trace gases on human breath. It involves the use of our selected ion flow tube (Sift) technique which we previously developed and used extensively for the study of gas phase ionic reactions occurring in ionized media such as the terrestrial atmosphere and interstellar gas clouds. Before discussing this analytical technique we describe the results of our very recent Sift and flowing afterglow (FA) studies of the reactions of the H3O+ and OH- ions, of their hydrates H3O+(H2O)1,2,3 and OH- (H2O)1,2, and of NO+ and O2+, with several hydrocarbons and oxygen-bearing organic molecules, studies that are very relevant to our trace gas analytical studies. Then follows a detailed discussion of the application of our Sift technique to trace gas analysis, after which we present some results obtained for the analyses of laboratory air, the breath of a healthy non-smoking person, the breath of a person who regularly smokes cigarettes, the complex vapours emitted by banana and onion, and the molecules present in a butane/air flame. We show how the quantitative analysis of breath can be achieved from only a single exhalation and in real time (the time response of the instrument is only about 20 ms). We also show how the time variation of breath gases over long time periods can be followed, using the decay of ethanol on the breath after the ingestion of distilled liquor as an example, yet simultaneously following several other trace gases including acetone and isoprene which are very easily detected on the breath of all individuals because of their relatively high partial pressures (typically 100 to 1000 ppb). The breath of a smoker is richer in complex molecules, some nitrogen containing organics apparently being very evident at the 5 to 50 ppb level

Noble gas isotopes and halogens in volatile-rich inclusions in diamonds

NASA Technical Reports Server (NTRS)

Burgess, Raymond; Turner, Grenville

1994-01-01

Application of the (40)Ar-(39)Ar method and noble gas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noble gas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.

Sensitivity of Tropospheric Chemical Composition to Halogen-Radical Chemistry Using a Fully Coupled Size-Resolved Multiphase Chemistry-Global Climate System: Halogen Distributions, Aerosol Composition, and Sensitivity of Climate-Relevant Gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, M.; Keene, W. C.; Easter, Richard C.

Observations and model studies suggest a significant but highly non-linear role for halogens, primarily Cl and Br, in multiphase atmospheric processes relevant to tropospheric chemistry and composition, aerosol evolution, radiative transfer, weather, and climate. The sensitivity of global atmospheric chemistry to the production of marine aerosol and the associated activation and cycling of inorganic Cl and Br was tested using a size-resolved multiphase coupled chemistry/global climate model (National Center for Atmospheric Research’s Community Atmosphere Model (CAM); v3.6.33). Simulation results showed strong meridional and vertical gradients in Cl and Br species. The simulation reproduced most available observations with reasonable confidence permittingmore » the formulation of potential mechanisms for several previously unexplained halogen phenomena including the enrichment of Br- in submicron aerosol, and the presence of a BrO maximum in the polar free troposphere. However, simulated total volatile Br mixing ratios were generally high in the troposphere. Br in the stratosphere was lower than observed due to the lack of long-lived organobromine species in the simulation. Comparing simulations using chemical mechanisms with and without reactive Cl and Br species demonstrated a significant temporal and spatial sensitivity of primary atmospheric oxidants (O3, HOx, NOx), CH4, and non-methane hydrocarbons (NMHC’s) to halogen cycling. Simulated O3 and NOx were globally lower (65% and 35%, respectively, less in the planetary boundary layer based on median values) in simulations that included halogens. Globally, little impact was seen in SO2 and non-sea-salt SO42- processing due to halogens. Significant regional differences were evident: The lifetime of nss-SO42- was extended downwind of large sources of SO2. The burden and lifetime of DMS (and its oxidation products) were lower by a factor of 5 in simulations that included halogens, versus those without, leading

Halogen degassing during ascent and eruption of water-poor basaltic magma

USGS Publications Warehouse

Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

2009-01-01

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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.

Regional atmospheric emissions determined from measurements at Jeju Island, Korea: Halogenated compounds from China

NASA Astrophysics Data System (ADS)

Kim, Jooil; Li, Shanlan; Kim, Kyung-Ryul; Stohl, Andreas; Mühle, Jens; Kim, Seung-Kyu; Park, Mi-Kyung; Kang, Dong-Jin; Lee, Gangwoong; Harth, Christina M.; Salameh, Peter K.; Weiss, Ray F.

2010-06-01

High-frequency in-situ measurements of a wide range of halogenated compounds including chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorinated compounds (PFCs), sulfur hexafluoride (SF6), and other chlorinated and brominated compounds have been made at Gosan (Jeju Island, Korea). Regional emissions of HCFC-22 (CHClF2) calculated from inverse modeling were combined with interspecies correlation methods to estimate national emissions for China, a major emitter of industrial halogenated gases. Our results confirm the signs of successful phase-out of primary ozone-depleting species such as CFCs, halons and many chlorinated or brominated compounds, along with substantial emissions of replacement HCFCs. Emissions derived for HFCs, PFCs, and SF6 were compared to published estimates and found to be a significant fraction of global totals. Overall, Chinese emissions of the halogenated compounds discussed here represent 19(14-17)% and 20(15-26)% of global emissions when evaluated in terms of their Ozone Depletion Potentials and 100-year Global Warming Potentials, respectively.

Halogen lamp experiment, HALEX

NASA Technical Reports Server (NTRS)

Schmitt, G.; Stapelmann, J.

1986-01-01

The main purpose of the Halogen Lamp Experiment (HALEX) was to investigate the operation of a halogen lamp during an extended period in a microgravity environment and to prove its behavior in space. The Mirror Heating Facilities for Crystal Growth and Material Science Experiments in space relies on one or two halogen lamps as a furnace to melt the specimens. The HALEX aim is to verify: full power operation of a halogen lamp for a period of about 60 hours; achievement of about 10% of its terrestrial life span; and operation of the halogen lamp under conditions similar to furnace operation.

The Halogen Bond

PubMed Central

2016-01-01

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

NASA Technical Reports Server (NTRS)

Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

2014-01-01

The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

LIDAR technology for measuring trace gases on Mars and Earth

NASA Astrophysics Data System (ADS)

Riris, H.; Abshire, J. B.; Graham, Allan; Hasselbrack, William; Rodriguez, Mike; Sun, Xiaoli; Weaver, Clark; Mao, Jianping; Kawa, Randy; Li, Steve; Numata, Kenji; Wu, Stewart

2017-11-01

Trace gases and their isotopic ratios in planetary atmospheres offer important but subtle clues as to the origins of a planet's atmosphere, hydrology, geology, and potential for biology. An orbiting laser remote sensing instrument is capable of measuring trace gases on a global scale with unprecedented accuracy, and higher spatial resolution that can be obtained by passive instruments. For Earth we have developed laser technique for the remote measurement of the tropospheric CO2, O2, and CH4 concentrations from space. Our goal is to develop a space instrument and mission approach for active CO2 measurements. Our technique uses several on and off-line wavelengths tuned to the CO2 and O2 absorption lines. This exploits the atmospheric pressure broadening of the gas lines to weigh the measurement sensitivity to the atmospheric column below 5 km and maximizes sensitivity to CO2 changes in the boundary layer where variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column use a selected region in the Oxygen A-band. Laser altimetry and atmospheric backscatter can also be measured simultaneously, which permits determining the surface height and measurements made to thick cloud tops and through aerosol layers. We use the same technique but with a different transmitter at 1.65 um to measure methane concentrations. Methane is also a very important trace gas on earth, and a stronger greenhouse gas than CO2 on a per molecule basis. Accurate, global observations are needed in order to better understand climate change and reduce the uncertainty in the carbon budget. Although carbon dioxide is currently the primary greenhouse gas of interest, methane can have a much larger impact on climate change. Methane levels have remained relatively constant over the last decade but recent observations in the Arctic have indicated that levels may be on the rise due to permafrost thawing. NASA's Decadal Survey underscored the importance of Methane as a

A study of atmospheric mixing of trace gases by aerial sampling with a multi-rotor drone

NASA Astrophysics Data System (ADS)

Chang, Chih-Chung; Chang, Chih-Yuan; Wang, Jia-Lin; Lin, Ming-Ren; Ou-Yang, Chang-Feng; Pan, Hsiang-Hsu; Chen, Yen-Chen

2018-07-01

We exploited a novel sampling vehicle, a multi-rotor drone carrying a remote-controlled whole air sampling device, to collect aerial samples with high sample integrity and preservation conditions. An array of 106 volatile organic compounds (VOCs), CO, CH4, and CO2 were analyzed and compared between the aerial samples (300-m height) and the ground-level samples in pairs to inspect for vertical mixing of the trace gases at a coastal site under three different meteorological conditions of local circulation, frontal passage, and high-pressure peripheral circulation. A rather homogeneous composition was observed for the sample pairs immediately after the frontal passage, indicating a well-mixed condition below 300 m. In contrast, inhomogeneous mixing was observed for the sample pairs under the other two conditions (local circulation and high-pressure peripheral circulation), suggesting different layers of air masses. Furthermore, information of unique source markers, composition profiles, and lifetimes of compounds were used to differentiate the origins of the air masses aloft and at the surface to substantiate the observed inhomogeneity. The study demonstrates that, with the availability of the near-surface aerial sampling coupling with in-laboratory analysis, detailed compositions of trace gases can now be readily obtained with superior data quality. Based on the distinctive chemical compositions, the sources, transport, and atmospheric mixing of the airborne pollutants in the near-surface atmosphere can be better studied and understood.

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Dilbert, C.A.

1984-01-01

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones. ?? 1984.

Source apportionment of particulate matter and trace gases near a major refinery near the Houston Ship Channel

NASA Astrophysics Data System (ADS)

Wallace, Henry W.; Sanchez, Nancy P.; Flynn, James H.; Erickson, Mathew H.; Lefer, Barry L.; Griffin, Robert J.

2018-01-01

From February 7 to 27, 2015, a mobile air quality laboratory was deployed to a location proximate to a major refinery, the Port of Houston, and several neighborhoods to conduct measurements of atmospheric trace gases and particulate matter. Two statistical models were utilized to apportion the sources of pollution impacting this site and the denizens of the nearby neighborhoods. Positive matrix factorization (PMF) was performed on the organic signal of the aerosol mass spectra, resulting in five factors totaling an average of 4.1 μg/m3 of the organic aerosol: hydrocarbon-like (0.67 μg/m3), cooking (0.35 μg/m3) biomass burning (1.14 μg/m3), low-volatility oxidized (1.15 μg/m3), and semi-volatile oxidized (0.78 μg/m3). Principal component analysis was performed on daytime and nighttime data, including concentrations from PMF output, of other PM1 components, and of trace gases. This generated five daytime and five nighttime factors that explained 74.5% and 73.0% of the variance, respectively. The most important factors impacting this site were from mobile source exhaust and petrochemical aromatic compound emissions. Together these two factors also constitute most of the observed carcinogens.

Carbon Dioxide Information Analysis Center and World Data Center for Atmospheric Trace Gases, Fiscal Year 2002 Annual Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cushman, R.M.

2003-08-28

The Carbon Dioxide Information Analysis Center (CDIAC), which includes the World Data Center (WDC) for Atmospheric Trace Gases, is the primary global change data and information analysis center of the U.S. Department of Energy (DOE). More than just an archive of data sets and publications, CDIAC has, since its inception in 1982, enhanced the value of its holdings through intensive quality assurance, documentation, and integration. Whereas many traditional data centers are discipline-based (for example, meteorology or oceanography), CDIAC's scope includes potentially anything and everything that would be of value to users concerned with the greenhouse effect and global climate change,more » including atmospheric concentrations and atmospheric emissions of carbon dioxide (CO{sub 2}) and other radiatively active gases; the role of the terrestrial biosphere and the oceans in the biogeochemical cycles of greenhouse gases; long-term climate trends; the effects of elevated CO{sub 2} on vegetation; and the vulnerability of coastal areas to rising sea levels.« less

Satellite Observations of Trace Gases and Their Application for Studying Air Quality Near Oil and Gas Operations

NASA Astrophysics Data System (ADS)

Kollonige, D. E.; Thompson, A. M.; Nichols, M.; Fasnacht, Z.; Martins, D. K.; Dickerson, R. R.

2014-12-01

The increase in the natural gas component of the energy sector has led many state and local municipalities to begin regulation of emissions from the oil and natural gas operators with air quality (AQ) as a concern. "Top-down" measurements of trace gases in the air above wells complement "bottom-up" inventories, used by EPA and AQ stakeholders, through a more accurate depiction of regional variability of methane and other species near and downwind of oil and gas operations. Satellite observations of methane, nitrogen dioxide, formaldehyde, ozone, and other carbon gases enhance the spatial and temporal coverage of the data needed to demonstrate any long-term impacts from shale gas development. As part of a NASA AQAST (Air Quality Applied Sciences Team) project, we are evaluating satellite measurements of trace gases in regions with oil and gas operations for their application as a "top-down" constraint. For validation of the satellite instruments' sensitivities to emitted gases, we focus on regions where the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) campaign deployed with ground and aircraft measurements, including, Maryland (2011), California and Texas (2013), and Colorado (2014). We compare vertical distributions of methane and volatile organic compounds (VOCs) nearby and downwind of oil and gas wells to locate any regional differences during the campaign time periods. This allows for better characterization of the satellite observations and their limitations for application in air quality studies in similar environments. Taking advantage of current EOS-era satellites' data records, we also analyze methane anomalies and gas correlations in the free troposphere from 2005 to present to identify trends for basins with oil and gas extraction sites and their influence on background concentrations downwind of wells. In most regions with oil and gas activity, we see continually

The contribution of hydrothermally altered ocean crust to the mantle halogen and noble gas cycles

NASA Astrophysics Data System (ADS)

Chavrit, Déborah; Burgess, Ray; Sumino, Hirochika; Teagle, Damon A. H.; Droop, Giles; Shimizu, Aya; Ballentine, Chris J.

2016-06-01

Recent studies suggest that seawater-derived noble gases and halogens are recycled into the deep mantle by the subduction of oceanic crust. To understand the processes controlling the availability of halogens and noble gases for subduction, we determined the noble gas elemental and isotopic ratios and halogen (Cl, Br, I) concentrations in 28 igneous samples from the altered oceanic crust (AOC) from 5 ODP sites in the Eastern and Western Pacific Ocean. Crushing followed by heating experiments enabled determination of noble gases and halogens in fluid inclusions and mineral phases respectively. Except for He and Ar, Ne, Kr and Xe isotopic ratios were all air-like suggesting that primary MORB signatures have been completely overprinted by air and/or seawater interaction. In contrast, 3He/4He ratios obtained by crushing indicate that a mantle helium component is still preserved, and 40Ar/36Ar values are affected by radiogenic decay in the mineral phases. The 130Xe/36Ar and 84Kr/36Ar ratios are respectively up to 15 times and 5 times higher than those of seawater and the highest ratios are found in samples affected by low temperature alteration (shallower than 800-900 m sub-basement). We consider three possible processes: (i) adsorption onto the clays present in the samples; (ii) fluid inclusions with a marine pore fluid composition; and (iii) fractionation of seawater through phase separation caused by boiling. Ninety percent of the Cl, Br and I were released during the heating experiments, showing that halogens are dominantly held in mineral phases prior to subduction. I/Cl ratios vary by 4 orders of magnitude, from 3 × 10-6 to 2 × 10-2. The mean Br/Cl ratio is 30% lower than in MORB and seawater. I/Cl ratios lower than MORB values are attributed to Cl-rich amphibole formation caused by hydrothermal alteration at depths greater than 800-900 m sub-basement together with different extents of I loss during low and high temperature alteration. At shallower depths, I

Spatial Variability of Trace Gases During DISCOVER-AQ: Planning for Geostationary Observations of Atmospheric Composition

NASA Technical Reports Server (NTRS)

Follette-Cook, Melanie B.; Pickering, K.; Crawford, J.; Appel, W.; Diskin, G.; Fried, A.; Loughner, C.; Pfister, G.; Weinheimer, A.

2015-01-01

Results from an in-depth analysis of trace gas variability in MD indicated that the variability in this region was large enough to be observable by a TEMPO-like instrument. The variability observed in MD is relatively similar to the other three campaigns with a few exceptions: CO variability in CA was much higher than in the other regions; HCHO variability in CA and CO was much lower; MD showed the lowest variability in NO2All model simulations do a reasonable job simulating O3 variability. For CO, the CACO simulations largely under over estimate the variability in the observations. The variability in HCHO is underestimated for every campaign. NO2 variability is slightly overestimated in MD, more so in CO. The TX simulation underestimates the variability in each trace gas. This is most likely due to missing emissions sources (C. Loughner, manuscript in preparation).Future Work: Where reasonable, we will use these model outputs to further explore the resolvability from space of these key trace gases using analyses of tropospheric column amounts relative to satellite precision requirements, similar to Follette-Cook et al. (2015).

Composition and Trends of Short-Lived Trace Gases in the UT/LS over Europe Observed by the CARIBIC Aircraft

NASA Astrophysics Data System (ADS)

Baker, A. K.; Brenninkmeijer, C. A.; Oram, D. E.; O'Sullivan, D. A.; Slemr, F.; Schuck, T. J.

2009-12-01

The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) involves the monthly deployment of an instrument container equipped to make atmospheric measurements from aboard a commercial airliner, and has operated since 2005 from aboard a Lufthansa Airbus 340-600 . Measurements from the container include in-situ trace gas and aerosol analyses and the collection of aerosol and whole air samples for post-flight laboratory analysis. Measurements made from the sampling flasks include greenhouse gas (GHG), halocarbon and nonmethane hydrocarbon (NMHC) analysis. CARIBIC flights originate in Frankfurt, Germany with routes to India, East Asia, South America, North America and Africa, and typical aircraft cruising altitudes of 10-12km allow for the monitoring of the upper troposphere/lower stratosphere (UT/LS) along these routes. Data collected during the aircraft’s departure from and return to Frankfurt provide a 4 year time series of near-monthly measurements of the composition of the UT/LS above Europe. Here we present a discussion of the composition of short-lived trace gases in the whole air samples collected above Europe during CARIBIC flights. Over 150 air samples were collected between May 2005 and July 2009, or about 4 samples per month. Of the whole air samples collected, about 45% showed influence by stratospheric air (i.e. very low values of GHG, NMHC and halocarbons, elevated O3, high potential vorticity). The remaining samples were representative of the upper troposphere; back trajectories for these samples indicate that a little over half were collected in air masses that had been in the boundary layer within the previous 8 days. The predominant source regions for these samples were the Gulf of Mexico and continental North America. Owing to their wide range of chemical lifetimes and the varying composition of emissions, short-lived trace gases transported to the UT/LS can be useful indicators of source

Exomars orbiter science and data-relay mission / looking for trace gases on Mars

NASA Astrophysics Data System (ADS)

Fratacci, Olivier

EXOMARS Orbiter Module: looking for trace gas on Mars and providing data relay support for future Mars Surface assets O.Fratacci, M.Mesrine, H.Renault, Thales Alenia Space France B.Musetti, M.Montagna, Thales Alenia Space Italy M.Kesselmann, M.Barczewski OHB P.Mitschdoerfer, D.Dellantonio Euro-pean Space Agency / ESTEC The European Space Agency (ESA) in a joint cooperation with NASA, will launch in 2016 the EXOMARS spacecraft composite to develop European landing technologies and provide a science orbiter with data-relay capability around Mars until end 2022. The spacecraft composite is composed of the Orbitr Module (OM), provided by TAS-France, an entry descent and landing demonstrator module (EDM) provided by TAS-Italy, and a set of six scientific payloads to be selected by the JPL during 2010. Recent observations of the planet Mars have indicated detection of methane as well as temporal, perhaps spatial variability in the detected signal while current photochemical models cannot explain the presence of methane in the atmosphere of Mars nor its reported rapid variations in space and time. The triple scientific objectives that drive the selection of these six instruments for the Exomars 2016 mission is to detect trace gases in Mars atmosphere, to characterise their spatial and temporal variation and to explore the source of the key trace gases (e.g. methane) on the surface. The launch is scheduled in January 2016 from Kennedy Space Center (KSC) using an ATLAS V 421 launcher with a total launch mass of 4.4 tons. After release of the EDM on Mars, the OM will perform the Mars Orbit Insertion manoeuvre and then reduce its elliptic orbit by implementing the first European Aerobraking around Mars for about 6 to 9 months, to finally end on a circular 400x400km orbit with an altitude in the range of 350km to 420km. From this orbit, a science phase will follow lasting 2 years in which the Mars atmosphere and surface is continuously observed. Science instruments composed of

Halogenation of microcapsule walls

NASA Technical Reports Server (NTRS)

Davis, T. R.; Schaab, C. K.; Scott, J. C.

1972-01-01

Procedure for halogenation of confining walls of both gelatin and gelatin-phenolic resin capsules is similar to that used for microencapsulation. Ten percent halogen content renders capsule wall nonburning; any higher content enhances flame-retardant properties of selected internal phase material. Halogenation decreases permeability of wall material to encapsulated materials.

Halogens, Barium and Uranium in Mantle Fluid Inclusions

NASA Astrophysics Data System (ADS)

Villa, I. M.; Peverelli, V.; Oglialoro, E.; Pettke, D. T.; Frezzotti, M. L.

2016-12-01

Halogens are an underexplored geochemical marker. A way to measure halogens at ng/g levels is measuring Ar, Kr and Xe in irradiated samples [1,2]. We derive absolute halogen amounts from rare gas amounts via scapolite monitor SY [2]. Kr-Xe systematics also yield Ba and U concentrations. We combined irradiation with stepheating on carbonate-sulfate-rich fluid inclusions (FI)-bearing xe­no­liths from El Hierro, Canarias: spinel harzburgite XML-7 and spinel dunite XML-1 [3]. Three components are recognized in the rare gas release. (1) Atmospheric surface contamination occurs up to 1000 °C. (2) FI decrepitation by laboratory heating occurs above 1200 °C [4], corresponding to the release of 80,82Kr and 128Xe in the 1200 and 1400 °C steps. Br whole-rock concentrations are 3-8 ng/g; the molar Br/Cl and I/Cl ratios in the harzburgite FI, 9 E-4 resp. 2 E-4, are identical to those in the dunite FI. This sets the halogens in our FI apart from MORB [2]. Halogen-derived rare gases are closely associated to artificial 131Xe from Ba; Ba has a high affinity of for CO2-rich fluids. Daughter minerals in multiphase FI were identified by Raman micro­spectroscopy [4]. The calculated Ba concentrations are 2-6 µg/g. (3) The third component is U-derived 134,136Xe and 86Kr released in a spike at 1000 °C, decoupled from FI. This requires a different carrier than FI, e.g. Ti oxides. As U concentrations are 10-20 pg/g, the U-bearing phase needs to be below a ppm, invisible by petro­graphy. The 136Xe/134Xe ratio > 1 suggests retention of radio­genic Xe. However, analysis of an unirradiated sample detected no radiogenic Xe. It is likely that Xe-U produced in the core of the McMaster reactor (thermal, epithermal and fast neutrons) has a different isotopic composition from that in textbooks, as proposed by [2].[1] Jeffery & Reynolds (1961) J.Geophys. Res. 66, 3582 [2] Kendrick (2012) Chem. Geol. 292, 116 [3] Oglialoro et al (2015) AGU Fall Meeting abstract V21C-3046 [4] Roedder (1965

Microwave limb sounder. [measuring trace gases in the upper atmosphere

NASA Technical Reports Server (NTRS)

Gustincic, J. J. (Inventor)

1981-01-01

Trace gases in the upper atmosphere can be measured by comparing spectral noise content of limb soundings with the spectral noise content of cold space. An offset Cassegrain antenna system and tiltable input mirror alternately look out at the limb and up at cold space at an elevation angle of about 22. The mirror can also be tilted to look at a black body calibration target. Reflection from the mirror is directed into a radiometer whose head functions as a diplexer to combine the input radiation and a local ocillator (klystron) beam. The radiometer head is comprised of a Fabry-Perot resonator consisting of two Fabry-Perot cavities spaced a number of half wavelengths apart. Incoming radiation received on one side is reflected and rotated 90 deg in polarization by the resonator so that it will be reflected by an input grid into a mixer, while the klystron beam received on the other side is also reflected and rotated 90 deg, but not without passing some energy to be reflected by the input grid into the mixer.

Tracing enhanced oil recovery signatures in casing gases from the Lost Hills oil field using noble gases

USGS Publications Warehouse

Barry, Peter H.; Kulongoski, Justin; Landon, Matthew K.; Tyne, R.L.; Gillespie, Janice; Stephens, Michael; Hillegonds, D.J.; Byrne, D.J.; Ballentine, C.J.

2018-01-01

Enhanced oil recovery (EOR) and hydraulic fracturing practices are commonly used methods to improve hydrocarbon extraction efficiency; however the environmental impacts of such practices remain poorly understood. EOR is particularly prevalent in oil fields throughout California where water resources are in high demand and disposal of high volumes of produced water may affect groundwater quality. Consequently, it is essential to better understand the fate of injected (EOR) fluids in California and other subsurface petroleum systems, as well as any potential effect on nearby aquifer systems. Noble gases can be used as tracers to understand hydrocarbon generation, migration, and storage conditions, as well as the relative proportions of oil and water present in the subsurface. In addition, a noble gas signature diagnostic of injected (EOR) fluids can be readily identified. We report noble gas isotope and concentration data in casing gases from oil production wells in the Lost Hills oil field, northwest of Bakersfield, California, and injectate gas data from the Fruitvale oil field, located within the city of Bakersfield. Casing and injectate gas data are used to: 1) establish pristine hydrocarbon noble-gas signatures and the processes controlling noble gas distributions, 2) characterize the noble gas signature of injectate fluids, 3) trace injectate fluids in the subsurface, and 4) construct a model to estimate EOR efficiency. Noble gas results range from pristine to significantly modified by EOR, and can be best explained using a solubility exchange model between oil and connate/formation fluids, followed by gas exsolution upon production. This model is sensitive to oil-water interaction during hydrocarbon expulsion, migration, and storage at reservoir conditions, as well as any subsequent modification by EOR.

Temperature Dependence of Dissociative Electron Attachment to Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Yicheng; Christophorou, Loucas G.

1996-10-01

Most of the gas mixtures currently in use for plasma processing of semiconductors involve halogenated hydrocarbons such as the strongly electronegative gases CCl4 and CFCl_3, the weakly electronegative gas CF_2Cl2 and the very weakly electronegative gases CHF3 and CF_4. Many dissociation processes are known to occur for these molecules. One of these dissociation reactions which is particularly effective for the strongly electronegative hydrocarbons is dissociative electron attachment. Even for weakly electron attaching gases, molecular dissociation via dissociative electron attachment at low energies can be an efficient dissociation process if the gas temperature is higher than ambient. Dissociative electron attachment is known to increase with increasing temperature above room temperature for many such compounds. In this paper, we report our measurements on the increases of the total electron attachment rate constant for CF_2Cl2 with increasing gas temperature from room temperature to about 600 K. -Research sponsored in part by the U.S. Air Force Wright Laboratory under contract F33615-96-C-2600 with the University of Tennessee. Also, Department of Physics, The University of Tennessee, Knoxville, TN.

Development and application of compact denuder sampling techniques with in situ derivatization followed by gas chromatography-mass spectrometry for halogen speciation in volcanic plumes

NASA Astrophysics Data System (ADS)

Rüdiger, Julian; Bobrowski, Nicole; Hoffmann, Thorsten

2015-04-01

Volcanoes are a large source for several reactive atmospheric trace gases including sulphur and halogen containing species. The detailed knowledge of volcanic plume chemistry can give insights into subsurface processes and can be considered as a useful geochemical tool for monitoring of volcanic activity, especially halogen to sulphur ratios (e.g. Bobrowski and Giuffrida, 2012; Donovan et al., 2014). The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable by UV spectrometers at a safe distance. Furthermore it is formed in the plume by a multiphase reaction mechanism under depletion of ozone in the plume. The abundance of BrO changes as a function of the reaction time and therefore distance from the vent as well as the spatial position in the plume. Due to the lack of analytical approaches for the accurate speciation of certain halogens (HBr, Br2, Br, BrCl, HOBr etc.) there are still uncertainties about the magnitude of volcanic halogen emissions and in particular their specificationtheir species and therefore also in the understanding of the bromine chemistry in volcanic plumes (Bobrowski et al., 2007). In this study, the first application of a 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated gas diffusion denuder (Huang and Hoffmann, 2008) on volcanic gases proved to be suitable to collect selectively gaseous bromine species with oxidation states of +1 or 0 (Br2 and BrO(H)), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with bromine gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. The diffusion denuder technique allows sampling of gaseous compounds exclusively without collecting particulate matter. Choosing a flow rate of 500 mL-min-1 and a denuder length of 0.5 m a nearly quantitative collection efficiency was achieved. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography

Measuring fluxes of trace gases and energy between ecosystems and the atmosphere - the state and future of the eddy covariance method.

PubMed

Baldocchi, Dennis

2014-12-01

The application of the eddy covariance flux method to measure fluxes of trace gas and energy between ecosystems and the atmosphere has exploded over the past 25 years. This opinion paper provides a perspective on the contributions and future opportunities of the eddy covariance method. First, the paper discusses the pros and cons of this method relative to other methods used to measure the exchange of trace gases between ecosystems and the atmosphere. Second, it discusses how the use of eddy covariance method has grown and evolved. Today, more than 400 flux measurement sites are operating world-wide and the duration of the time series exceed a decade at dozens of sites. Networks of tower sites now enable scientists to ask scientific questions related to climatic and ecological gradients, disturbance, changes in land use, and management. The paper ends with discussions on where the field of flux measurement is heading. Topics discussed include role of open access data sharing and data mining, in this new era of big data, and opportunities new sensors that measure a variety of trace gases, like volatile organic carbon compounds, methane and nitrous oxide, and aerosols, may yield. © 2014 John Wiley & Sons Ltd.

An approach for retrieval of atmospheric trace gases CO II, CH 4 and CO from the future Canadian micro earth observation satellite (MEOS)

NASA Astrophysics Data System (ADS)

Trishchenko, Alexander P.; Khlopenkov, Konstantin V.; Wang, Shusen; Luo, Yi; Kruzelecky, Roman V.; Jamroz, Wes; Kroupnik, Guennadi

2007-10-01

Among all trace gases, the carbon dioxide and methane provide the largest contribution to the climate radiative forcing and together with carbon monoxide also to the global atmospheric carbon budget. New Micro Earth Observation Satellite (MEOS) mission is proposed to obtain information about these gases along with some other mission's objectives related to studying cloud and aerosol interactions. The miniature suit of instruments is proposed to make measurements with reduced spectral resolution (1.2nm) over wide NIR range 0.9μm to 2.45μm and with high spectral resolution (0.03nm) for three selected regions: oxygen A-band, 1.5μm-1.7μm band and 2.2μm-2.4μm band. It is also planned to supplement the spectrometer measurements with high spatial resolution imager for detailed characterization of cloud and surface albedo distribution within spectrometer field of view. The approaches for cloud/clear-sky identification and column retrievals of above trace gases are based on differential absorption technique and employ the combination of coarse and high-resolution spectral data. The combination of high and coarse resolution spectral data is beneficial for better characterization of surface spectral albedo and aerosol effects. An additional capability for retrieval of the vertical distribution amounts is obtained from the combination of nadir and limb measurements. Oxygen A-band path length will be used for normalization of trace gas retrievals.

Measurements of Trace Gases in the Tropical Tropopause Layer

NASA Technical Reports Server (NTRS)

Marcy, T. P.; Popp, P. J.; Gao, R. S.; Fahey, D. W.; Ray, E. A.; Richard, E. C.; Thompson, T. L.; Atlas, E. L.; Lowenstein, M.; Wofsy, S. C.;

Quantification of Aerosol Derived Particulate Matter and Trace gases in the Coastal Belt of Kochi, Kerala, India

NASA Astrophysics Data System (ADS)

H, S. C.

2016-02-01

Aerosol chemistry is a window to unravel the various environmental health hazard problems. This open forum which deals with the study of formation, interaction, transformation of aerosol species, which could enable in the assessment of biogeochemical cycling of anthropogenic and toxic species. It also preserves the temperature balance and reservoir and sink for nutrients, trace metals and organic species. An inventory of air pollutants is a proactive and necessary first step towards the control of air pollution. Surveys and studies on the sources of pollution and their apportionment to different sources are a pre-requisite for alleviating environmental disorder. The Kochi City (The Queen of Arabian Sea), Kerala, India is a fast growing industrial region where mounting urbanization has been affecting the quality of the atmospheric environment. Cochin estuarine environment is progressively affected by marine pollution concomitant by industrial hazardous chemicals and municipal waste. Further, rapid urbanization and industrialization has lead to lofting and large scale advection of these omnipresent species in the atmosphere. Studies were conducted to assess the significance and potential impact occupied to these ubiquitous species. The major gaseous pollutants include gases like sulphur dioxide, nitrogen dioxide, ammonia and particulate matter (PM). An attempt was performed to unravel the inorganic species in the atmosphere and programmed by means of quantification of PM10 and trace gases. Their distribution pattern and outcomes are inferred.

Atmos/Atlas 3 Infrared Profile Measurements of Trace Gases in The November 1994 Tropical and Subtropical Upper Troposphere

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Gunson, M. R.; Wang, P.-H.; Arduini, R. F.; Baum, B. A.; Minnis, P.; Minnis, P.; Goldman, A.; Abrams, M. C.; Zander, R.;

History of chemically and radiatively important atmospheric gases from the Advanced Global Atmospheric Gases Experiment (AGAGE)

NASA Astrophysics Data System (ADS)

Prinn, Ronald G.; Weiss, Ray F.; Arduini, Jgor; Arnold, Tim; Langley DeWitt, H.; Fraser, Paul J.; Ganesan, Anita L.; Gasore, Jimmy; Harth, Christina M.; Hermansen, Ove; Kim, Jooil; Krummel, Paul B.; Li, Shanlan; Loh, Zoë M.; Lunder, Chris R.; Maione, Michela; Manning, Alistair J.; Miller, Ben R.; Mitrevski, Blagoj; Mühle, Jens; O'Doherty, Simon; Park, Sunyoung; Reimann, Stefan; Rigby, Matt; Saito, Takuya; Salameh, Peter K.; Schmidt, Roland; Simmonds, Peter G.; Steele, L. Paul; Vollmer, Martin K.; Wang, Ray H.; Yao, Bo; Yokouchi, Yoko; Young, Dickon; Zhou, Lingxi

2018-06-01

We present the organization, instrumentation, datasets, data interpretation, modeling, and accomplishments of the multinational global atmospheric measurement program AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE is distinguished by its capability to measure globally, at high frequency, and at multiple sites all the important species in the Montreal Protocol and all the important non-carbon-dioxide (non-CO2) gases assessed by the Intergovernmental Panel on Climate Change (CO2 is also measured at several sites). The scientific objectives of AGAGE are important in furthering our understanding of global chemical and climatic phenomena. They are the following: (1) to accurately measure the temporal and spatial distributions of anthropogenic gases that contribute the majority of reactive halogen to the stratosphere and/or are strong infrared absorbers (chlorocarbons, chlorofluorocarbons - CFCs, bromocarbons, hydrochlorofluorocarbons - HCFCs, hydrofluorocarbons - HFCs and polyfluorinated compounds (perfluorocarbons - PFCs), nitrogen trifluoride - NF3, sulfuryl fluoride - SO2F2, and sulfur hexafluoride - SF6) and use these measurements to determine the global rates of their emission and/or destruction (i.e., lifetimes); (2) to accurately measure the global distributions and temporal behaviors and determine the sources and sinks of non-CO2 biogenic-anthropogenic gases important to climate change and/or ozone depletion (methane - CH4, nitrous oxide - N2O, carbon monoxide - CO, molecular hydrogen - H2, methyl chloride - CH3Cl, and methyl bromide - CH3Br); (3) to identify new long-lived greenhouse and ozone-depleting gases (e.g., SO2F2, NF3, heavy PFCs (C4F10, C5F12, C6F14, C7F16, and C8F18) and hydrofluoroolefins (HFOs; e.g., CH2 = CFCF3) have been identified in AGAGE), initiate the real-time monitoring of these new gases, and reconstruct their past histories from AGAGE, air archive, and firn air measurements; (4) to determine the average concentrations and

Top-down emission estimation of European sources of halogenated hydrocarbons using a Kalman-filter based inversion

NASA Astrophysics Data System (ADS)

Brunner, Dominik; Henne, Stephan; Keller, Christoph A.; Reimann, Stefan; Vollmer, Martin K.; O'Doherty, Simon

2010-05-01

Halogenated hydrocarbons in the atmosphere are mostly synthetic products of the chemical industry designed for a wide range of applications. The first generation of compounds, the bromine- and chlorine-containing halons and chlorofluorocarbons (CFCs), were shown to be harmful to the stratospheric ozone layer. This motivated the international community to initiate the Montreal Protocol in 1987 to phase out their production globally. In the industrialized countries CFCs were consequently replaced by the shorter-lived hydrochlorofluorocarbons (HCFCs) during the 1990s and thereafter by the completely chlorine-free HFCs. Although not harmful to the ozone layer anymore, some of the HFCs are potent greenhouse gases and are therefore regulated under the Kyoto Protocol. The high-alpine station Jungfraujoch and the coastal station Mace Head are two of only four sites of the European SOGE network (System for Observation of Halogenated Greenhouse Gases in Europe) with high-frequency measurements of halogenated compounds. Based on observations at these two sites, we here present a combined measurement - model analysis of the distribution of European emissions for a selection of compounds, and trace their evolution with time since measurements started in 2000. For the spatial allocation of sources, the measurements were combined with detailed transport simulations. For a qualitative allocation of sources in Europe we employed the trajectory statistics method of Seibert et al. (1994) and Stohl (1996). For Mace Head trajectories were computed with the FLEXPART model driven by ECMWF analyzed winds at 1°x1° resolution. For the station Jungfraujoch, however, we used the model COSMO-TRAJ driven by high-resolution wind fields (7 km x 7 km) of the weather forecast model COSMO of MeteoSwiss in order to better represent the transport in complex topography over the Alps. The method allows identifying the major source regions of the different compounds in Western and Central Europe. The

Passive degassing at Nyiragongo (D.R. Congo) and Etna (Italy) volcanoes: the chemical characterization of the emissions and assessment of their uptake of trace elements emissions on the local environment

NASA Astrophysics Data System (ADS)

Calabrese, Sergio; Scaglione, Sarah; Milazzo, Silvia; D'Alessandro, Walter; Bobrowski, Nicole; Giuffrida, Giovanni; Tedesco, Dario; Parello, Francesco

2014-05-01

Volcanoes are well known as an impressive large natural source of trace elements into the troposphere. Among others, Etna (Italy) and Nyiragongo (D.R. Congo), two noteworthy emitters on Earth, are two stratovolcanoes located in different geological settings, both characterized by persistent passive degassing from their summit craters. Here, we present some results on trace element composition in volcanic plume emissions, atmospheric bulk deposition (rainwater) and their uptake of the surrounding vegetation, with the aim to compare and identify differences and similarities between this these two volcanoes. Volcanic emissions were sampled by using active filter-pack for acid gases (sulfur and halogens) and specific teflon filters for particulates (major and trace elements). The impact of the volcanogenic deposition in the surrounding of the crater rims was investigated by using different sampling techniques: bulk rain collectors gauges were used to collect atmospheric bulk deposition, and biomonitoring technique was carried out to collect gases and particulates by using endemic plant species. Concentrations of major and trace elements of volcanic plume emissions (gases and particulates) were obtained by elution and microwave digestion of the collected filters: sulfur and halogens were determined by ion chromatography and ICP-MS, and untreated filters for particulate were acid digested and analysed by ICP-OES and ICP-MS. Rain water and plant samples were also analysed for major and trace elements by using ICP-OES and ICP-MS. In total 55 elements were determined. The estimates of the trace element fluxes confirm that Etna and Nyiragongo are large sources of metals to the atmosphere, especially considering their persistent state of passive degassing. In general, chemical composition of the volcanic aerosol particles of both volcanoes is characterized by two main components: one is related to the silicic component produced by magma bursting and fragmentation, enriching

The airborne mass spectrometer AIMS - Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

NASA Astrophysics Data System (ADS)

Jurkat, T.; Kaufmann, S.; Voigt, C.; Schäuble, D.; Jeßberger, P.; Ziereis, H.

2015-12-01

Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulphur components. The Airborne chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using chemical ionization with SF5- reagent ions for the simultaneous measurement of trace gas concentrations in the pptv to ppmv (10-12 to 10-6 mol mol-1) range of HCl, HNO3 and SO2 with in-flight and online calibration called AIMS-TG. Part 1 of this paper (Kaufmann et al., 2015) reports on the UTLS water vapour measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed generating a characteristic ionization scheme. HNO3 and HCl are routinely calibrated in-flight using permeation devices, SO2 is permanently calibrated during flight adding an isotopically labelled 34SO2 standard. In addition, we report on trace gas measurements of HONO which is sensitive to the reaction with SF5-. The detection limit for the various trace gases is in the low ten pptv range at a 1 s time resolution with an overall uncertainty of the measurement in the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO. Exemplarily, measurements conducted during the TACTS/ESMVal mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. Comparison of AIMS measurements with other measurement techniques allow to draw a comprehensive

OH reactivity and potential SOA yields from volatile organic compounds and other trace gases measured in controlled laboratory biomass burns

Treesearch

J. B. Gilman; C. Warneke; W. C. Kuster; P. D. Goldan; P. R. Veres; J. M. Roberts; J. A. de Gouw; I. R. Burling; R. J. Yokelson

2010-01-01

A comprehensive suite of instruments were used to characterize volatile organic compounds (VOCs) and other trace gases (e.g., CO, CH4, NO2, etc.) emitted from controlled burns of various fuel types common to the Southeastern and Southwestern United States. These laboratory-based measurements were conducted in February 2009 at the U.S. Department of Agriculture’s Fire...

Analysis and Modeling of Trace Gases and Aerosols in Severe Convection: The 22 June 2012 DC3 Case

NASA Astrophysics Data System (ADS)

Barth, M. C.; Apel, E. C.; Bela, M.; Fried, A.; Fuchs, B.; Pickering, K. E.; Pollack, I. B.; Rutledge, S. A.

2016-12-01

The Deep Convective Clouds and Chemistry (DC3) field campaign aimed to quantify and characterize the dynamics, physics, lightning, and transport of trace gases and aerosols in convection, as well as the chemical aging of convective outflow plumes in the upper troposphere. These goals were met by deploying radars, lightning mapping arrays, weather balloons, and aircraft to sample storms in northeast Colorado, west Texas to central Oklahoma, and northern Alabama. Here, we use one case, 22 June 2012 severe convection in northeast Colorado and southwest Nebraska, as an example for quantifying and predicting convective transport of trace gases and aerosols, lightning flash rate, lightning production of nitrogen oxides, and subsequent ozone production downwind of the storms. This case was unique in that one severe storm ingested a wildfire smoke plume at 7 km altitude while other storms in the area did not. Several analyses of this case have been done using the aircraft composition measurements, dual-Doppler and polarimetric radar products, and lightning mapping array data. It was determined that the storm unaffected by the High Park fire smoke plume had a 4.8±0.9%/km entrainment rate and estimated scavenging efficiencies of CH2O, H2O2, CH3OOH, SO2, and HNO3 of 41±4%, 79±19, 44±47%, 92±4%, 95±12%, respectively. Total (intracloud and cloud-to-ground) lightning flash rates were 98-106 flashes per minute when the aircraft were sampling the outflow of the storms, resulting in an estimate of lightning-NOx production of 142±25 moles NO per flash. Box modeling simulations estimate the production of O3 in the convective outflow of these storms to be 11-14 ppbv over 2 days. These results are used to evaluate the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to learn how well a state-of-the-art model represents the storm processing of trace gases. The WRF-Chem simulations are analyzed further to examine the effect of aerosols in the smoke plume on

Origin, speciation, and fluxes of trace-element gases at Augustine volcano, Alaska: Insights into magma degassing and fumarolic processes

NASA Astrophysics Data System (ADS)

Symonds, Robert B.; Reed, Mark H.; Rose, William I.

1992-02-01

Thermochemical modeling predicts that trace elements in the Augustine gas are transported from near-surface magma as simple chloride (NaCl, KCl, FeCl 2, ZnCl 2, PbCl 2, CuCl, SbCl 3, LiCl, MnCl 2, NiCl 2, BiCl, SrCl 2), oxychloride (MoO 2Cl 2), sulfide (AsS), and elemental (Cd) gas species. However, Si, Ca, Al, Mg, Ti, V, and Cr are actually more concentrated in solids, beta-quartz (SiO 2), wollastonite (CaSiO 3), anorthite (CaAl 2Si 2O 8), diopside (CaMgSi 2O 6), sphene (CaTiSiO 5), V 2O 3(c), and Cr 2O 3(c), respectively, than in their most abundant gaseous species, SiF 4, CaCl 2, AlF 2O, MgCl 2 TiCl 4, VOCl 3, and CrO 2Cl 2. These computed solids are not degassing products, but reflect contaminants in our gas condensates or possible problems with our modeling due to "missing" gas species in the thermochemical data base. Using the calculated distribution of gas species and the COSPEC SO 2 fluxes, we have estimated the emission rates for many species (e.g., COS, NaCl, KCl, HBr, AsS, CuCl). Such forecasts could be useful to evaluate the effects of these trace species on atmospheric chemistry. Because of the high volatility of metal chlorides (e.g., FeCl 2, NaCl, KCl, MnCl 2, CuCl), the extremely HCl-rich Augustine volcanic gases are favorable for transporting metals from magma. Thermochemical modeling shows that equilibrium degassing of magma near 870°C can account for the concentrations of Fe, Na, K, Mn, Cu, Ni and part of the Mg in the gases escaping from the dome fumaroles on the 1986 lava dome. These calculations also explain why gases escaping from the lower temperature but highly oxidized moat vents on the 1976 lava dome should transport less Fe, Na, K, Mn and Ni, but more Cu; oxidation may also account for the larger concentrations of Zn and Mo in the moat gases. Nonvolatile elements (e.g., Al, Ca, Ti, Si) in the gas condensates came from eroded rock particles that dissolved in our samples or, for Si, from contamination from the silica sampling tube. Only a

Oil and gas exploration system and method for detecting trace amounts of hydrocarbon gases in the atmosphere

DOEpatents

Wamsley, Paula R.; Weimer, Carl S.; Nelson, Loren D.; O'Brien, Martin J.

2003-01-01

An oil and gas exploration system and method for land and airborne operations, the system and method used for locating subsurface hydrocarbon deposits based upon a remote detection of trace amounts of gases in the atmosphere. The detection of one or more target gases in the atmosphere is used to indicate a possible subsurface oil and gas deposit. By mapping a plurality of gas targets over a selected survey area, the survey area can be analyzed for measurable concentration anomalies. The anomalies are interpreted along with other exploration data to evaluate the value of an underground deposit. The system includes a differential absorption lidar (DIAL) system with a spectroscopic grade laser light and a light detector. The laser light is continuously tunable in a mid-infrared range, 2 to 5 micrometers, for choosing appropriate wavelengths to measure different gases and avoid absorption bands of interference gases. The laser light has sufficient optical energy to measure atmospheric concentrations of a gas over a path as long as a mile and greater. The detection of the gas is based on optical absorption measurements at specific wavelengths in the open atmosphere. Light that is detected using the light detector contains an absorption signature acquired as the light travels through the atmosphere from the laser source and back to the light detector. The absorption signature of each gas is processed and then analyzed to determine if a potential anomaly exists.

Photochemical parameters of atmospheric source gases: accurate determination of OH reaction rate constants over atmospheric temperatures, UV and IR absorption spectra

NASA Astrophysics Data System (ADS)

Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.

2012-12-01

The emissions of halogenated (Cl, Br containing) organics of both natural and anthropogenic origin contribute to the balance of and changes in the stratospheric ozone concentration. The associated chemical cycles are initiated by the photochemical decomposition of the portion of source gases that reaches the stratosphere. Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound lifetime in the troposphere and release of active halogen in the stratosphere for a majority of halogen source gases. Therefore, the accuracy of photochemical data is of primary importance for the purpose of comprehensive atmospheric modeling and for simplified kinetic estimations of global impacts on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP). The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still may constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the presentation is to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. A detailed inventory of accountable sources of

Detection of Matrix Elements and Trace Impurities in Cu(In, Ga)Se2 Photovoltaic Absorbers Using Surface Analytical Techniques.

PubMed

Kim, Min Jung; Lee, Jihye; Kim, Seon Hee; Kim, Haidong; Lee, Kang-Bong; Lee, Yeonhee

2015-10-01

Chalcopyrite Cu(In, Ga)Se2 (CIGS) thin films are well known as the next-generation solar cell materials notable for their high absorption coefficient for solar radiation, suitable band gap, and ability for deposition on flexible substrate materials, allowing the production of highly flexible and lightweight solar panels. To improve solar cell performances, a quantitative and depth-resolved elemental analysis of photovoltaic thin films is much needed. In this study, Cu(In, Ga)Se2 thin films were prepared on molybdenum back contacts deposited on soda-lime glass substrates via three-stage evaporation. Surface analyses via AES and SIMS were used to characterize the CIGS thin films and compare their depth profiles. We determined the average concentration of the matrix elements, Cu, In, Ga, and Se, using ICP-AES, XRF, and EPMA. We also obtained depth profiling results using TOF-SIMS, magnetic sector SIMS and AES, and APT, a sub-nanometer resolution characterization technique that enables three-dimensional elemental mapping. The SIMS technique, with its high detection limit and ability to obtain the profiles of elements in parallel, is a powerful tool for monitoring trace elements in CIGS thin films. To identify impurities in a CIGS layer, the distribution of trace elements was also observed according to depth by SIMS and APT.

Knudsen cell: Investigations about the uptake of important traces gases on ambient airborne mineral dust

NASA Astrophysics Data System (ADS)

Horn, Sabrina; Herrmann, Hartmut

2013-04-01

Mineral dust constitutes one of the largest mass fractions of natural aerosol. Its emission is estimated between 800 - 2000 Tg/a]. The dust is emitted through sand and dust storms in the arid regions of our planet, in particular by the great desserts such as the Sahara. The complex chemical composition of mineral dust is similar to crust material, because the dust is produced by soil erosion. The main components of mineral dust are SiO2 and Al2O3, whereas the active oxides (Fe2O3, TiO2) show some variety in content due to the dust source region. Mineral dust particles can be transported over several 1000 km and during its transport the surface can be changed by the uptake of water vapor and trace gases. On such modified surfaces homo- and heterogeneous reactions can occur. Trace gas uptakes play an important role in atmospheric chemistry as sinks or sources for several gaseous species. Hence, it is necessary to study these reactions. Among several experimental setups, the Knudsen cell is one of the promising tools to study reactive uptakes from the gas phase and the release of products formed by dust surface-mediated reactions. The Knudsen cell, implemented by Golden et al. in 1975, is a high vacuum flow reactor operating under molecular flow conditions, i.e., gas-wall collisions are highly preferred over gas-gas collisions. Despite several Knudsen cell studies examining the reaction between different traces gases and model dust surfaces constituted of not more than a few components, no measurements utilizing collected ambient mineral dust are done so far. For a better understanding of the chemistry on mineral dust surfaces gas uptake measurements will be done with a Knudsen cell. The first measurements are done with isopropanol on TiO2. Afterwards there are studies with different substrates like, Al2O3 (α- and γ-phase), FeO2, Arizona test dust, air collected mineral dust from the Cap Verde islands. In the beginning SO2, NO2 and HNO3 will be used.

Analysis of gaseous SO2, CO2 and halogen species in volcanic plumes using a multirotor Unmanned Aerial Vehicle (UAV).

NASA Astrophysics Data System (ADS)

Rüdiger, J.; de Moor, M. J.; Tirpitz, L.; Bobrowski, N.; Gutmann, A.; Hoffmann, T.

2016-12-01

Volcanoes are a large source for several reactive atmospheric trace gases including sulfur and halogen containing species. The detailed understanding of volcanic plume chemistry is needed to draw information from gas measurements on subsurface processes. This knowledge is essential for using gas measurements as a monitoring tool for volcanic activity. The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable from safe distance by spectroscopic remote sensing techniques. BrO is not directly emitted, but is formed in the plume by a multiphase reaction mechanism. The abundance of BrO changes as a function of the distance from the vent as well as the spatial position in the plume. The precursor substance for the formation of BrO is HBr with Br2 as an intermediate product. In this study we present the application of a UAV as a carrier for a remote-controlled sampling system for halogen species (Br2, HBr, BrCl, etc), based on the gas diffusion denuder technique, which allows speciation and enrichment by selective organic reactions. For the analysis of gaseous SO2 and CO2 an in-situ gas monitoring system was additionally mounted. This setup was deployed into the gas plumes of Stromboli Volcano (Italy) and Masaya Volcano (Nicaragua) in 2016, to investigate the halogen chemistry at distant locations in the plume further downwind to the emission source, which are in most cases not accessible by other approaches. The used quadrocopter (0.75 m in diameter) weighs 2.45 kg and lifts a payload of 1.3 kg. Flights into the plume were conducted with ascents of up to 900 m, starting at 500 to 800 m altitude. From telemetrically transmitted SO2 mixing ratios, areas of dense plume were localized to keep the UAV stationary for up to 10 minutes of sampling time. Herein we will present time and spatial resolved gas mixing ratio data for SO2, CO2 and halogen species for a downwind plume age of about 3 to 5 minutes.

Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

PubMed

Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

2016-11-23

The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

PubMed

Beauchamp, Guy

2008-10-23

This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

The noble gases: how their electronegativity and hardness determines their chemistry.

PubMed

Furtado, Jonathan; De Proft, Frank; Geerlings, Paul

2015-02-26

The establishment of an internally consistent scale of noble gas electronegativities is a long-standing problem. In the present study, the problem is attacked via the Mulliken definition, which in recent years gained widespread use to its natural appearance in the context of conceptual density functional theory. Basic ingredients of this scale are the electron affinity and the ionization potential. Whereas the latter can be computed routinely, the instability of the anion makes the judicious choice of computational technique for evaluating electron affinities much more tricky. We opted for Puiatti's approach, extrapolating the energy of high ε solvent stabilized anions to the ε = 1 (gas phase) case. The results give negative electron affinity values, monotonically increasing (except for helium which is an outlier in most of the story) to almost zero at eka-radon in agreement with high level calculations. The stability of the B3LYP results is successfully tested both via improving the level of theory (CCSD(T)) and expanding the basis set. Combined with the ionization energies (in good agreement with experiment), an electronegativity scale is obtained displaying (1) a monotonic decrease of χ when going down the periodic table, (2) top values not for the noble gases but for the halogens, as opposed to most (extrapolation) procedures of existing scales, invariably placing the noble gases on top, and (3) noble gases having electronegativities close to the chalcogens. In the accompanying hardness scale (hardly, if ever, discussed in the literature) the noble gases turn out to be by far the farthest the hardest elements, again with a continuous decrease with increasing Z. Combining χ value of the halogens and the noble gases the Ng(δ+)F(δ-) bond polarity emerging from ab initio calculations naturally emerges. In conclusion, the chemistry of the noble gases is for a large part determined by their extreme hardness, equivalent to a high resistance to change in its

Characteristics of Fine Particles in an Urban Atmosphere-Relationships with Meteorological Parameters and Trace Gases.

PubMed

Zhang, Tianhao; Zhu, Zhongmin; Gong, Wei; Xiang, Hao; Fang, Ruimin

2016-08-10

Atmospheric fine particles (diameter < 1 μm) attract a growing global health concern and have increased in urban areas that have a strong link to nucleation, traffic emissions, and industrial emissions. To reveal the characteristics of fine particles in an industrial city of a developing country, two-year measurements of particle number size distribution (15.1 nm-661 nm), meteorological parameters, and trace gases were made in the city of Wuhan located in central China from June 2012 to May 2014. The annual average particle number concentrations in the nucleation mode (15.1 nm-30 nm), Aitken mode (30 nm-100 nm), and accumulation mode (100 nm-661 nm) reached 4923 cm(-3), 12193 cm(-3) and 4801 cm(-3), respectively. Based on Pearson coefficients between particle number concentrations and meteorological parameters, precipitation and temperature both had significantly negative relationships with particle number concentrations, whereas atmospheric pressure was positively correlated with the particle number concentrations. The diurnal variation of number concentration in nucleation mode particles correlated closely with photochemical processes in all four seasons. At the same time, distinct growth of particles from nucleation mode to Aitken mode was only found in spring, summer, and autumn. The two peaks of Aitken mode and accumulation mode particles in morning and evening corresponded obviously to traffic exhaust emissions peaks. A phenomenon of "repeated, short-lived" nucleation events have been created to explain the durability of high particle concentrations, which was instigated by exogenous pollutants, during winter in a case analysis of Wuhan. Measurements of hourly trace gases and segmental meteorological factors were applied as proxies for complex chemical reactions and dense industrial activities. The results of this study offer reasonable estimations of particle impacts and provide references for emissions control strategies in industrial cities of developing

Characteristics of Fine Particles in an Urban Atmosphere—Relationships with Meteorological Parameters and Trace Gases

PubMed Central

Zhang, Tianhao; Zhu, Zhongmin; Gong, Wei; Xiang, Hao; Fang, Ruimin

2016-01-01

Atmospheric fine particles (diameter < 1 μm) attract a growing global health concern and have increased in urban areas that have a strong link to nucleation, traffic emissions, and industrial emissions. To reveal the characteristics of fine particles in an industrial city of a developing country, two-year measurements of particle number size distribution (15.1 nm–661 nm), meteorological parameters, and trace gases were made in the city of Wuhan located in central China from June 2012 to May 2014. The annual average particle number concentrations in the nucleation mode (15.1 nm–30 nm), Aitken mode (30 nm–100 nm), and accumulation mode (100 nm–661 nm) reached 4923 cm−3, 12193 cm−3 and 4801 cm−3, respectively. Based on Pearson coefficients between particle number concentrations and meteorological parameters, precipitation and temperature both had significantly negative relationships with particle number concentrations, whereas atmospheric pressure was positively correlated with the particle number concentrations. The diurnal variation of number concentration in nucleation mode particles correlated closely with photochemical processes in all four seasons. At the same time, distinct growth of particles from nucleation mode to Aitken mode was only found in spring, summer, and autumn. The two peaks of Aitken mode and accumulation mode particles in morning and evening corresponded obviously to traffic exhaust emissions peaks. A phenomenon of “repeated, short-lived” nucleation events have been created to explain the durability of high particle concentrations, which was instigated by exogenous pollutants, during winter in a case analysis of Wuhan. Measurements of hourly trace gases and segmental meteorological factors were applied as proxies for complex chemical reactions and dense industrial activities. The results of this study offer reasonable estimations of particle impacts and provide references for emissions control strategies in industrial cities of

Marine cycling of the climate relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2) in the Peruvian upwelling regime

NASA Astrophysics Data System (ADS)

Lennartz, Sinikka; von Hobe, Marc; Booge, Dennis; Gonçalves-Araujo, Rafael; Bracher, Astrid; Röttgers, Rüdiger; Ksionzek, Kerstin B.; Koch, Boris P.; Fischer, Tim; Bittig, Henry; Quack, Birgit; Krüger, Kirstin; Marandino, Christa A.

2017-04-01

The ocean is a major source for the climate relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2). While the greenhouse gas CS2 quickly oxidizes to OCS in the atmosphere, the atmospheric lifetime of OCS of 2-7 years leads to an accumulation of this gas and makes it the most abundant reduced sulfur compound in the atmosphere. OCS has a counteracting effect on the climate: in the troposphere, it acts as a greenhouse gas causing warming, whereas it also sustains the stratospheric aerosol layer, and thus increases Earth's albedo causing cooling. To better constrain the important oceanic source of these trace gases, the marine cycling needs to be well understood and quantified. For OCS, the production and consumption processes are identified, but photoproduction and light-independent production rates remain to be quantified across different regions. In contrast, the processes that influence the oceanic cycling of CS2 are less well understood. Here we present new data from a cruise to the Peruvian upwelling regime and relate measurements of OCS and CS2 to key parameters, such as dissolved organic sulfur, chromophoric and fluorescent dissolved organic matter. We use a 1D water column model to further constrain their production and degradation rates. A focus is set on the influence of oxygen on the marine cycling of these two gases in oxygen depleted zones in the ocean, which are expected to expand in the future.

Halogen Chemistry in the CMAQ Model

EPA Science Inventory

Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

Observations of tropospheric trace gases from GOSAT thermal infrared spectra

NASA Astrophysics Data System (ADS)

Ohyama, Hirofumi; Shiomi, Kei; Kawakami, Shuji; Nakajima, Masakatsu; Maki, Takashi; Deushi, Makoto

2013-04-01

Thermal And Near infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS), which is one of the sensors onboard the Greenhouse gases Observing SATellite (GOSAT), measures the sunlight backscattered by the Earth's surface and atmosphere as well as the thermal radiance emitted from the Earth. Atmospheric trace gases such as ozone (O3), water vapor (H2O and HDO), methanol (CH3OH) and ammonia (NH3) are derived from the thermal infrared spectral radiance recorded with the TANSO-FTS by an optimal estimation retrieval approach. TANSO-FTS total ozone columns are compared with Dobson spectrophotometer and Ozone Monitoring Instrument (OMI) data. The TANSO-FTS total ozone retrievals exhibit a positive bias of 3-4% with a root-mean-square difference of 2-6% compared to the Dobson and OMI measurements. We compare TANSO-FTS tropospheric ozone columns to those from ozonesonde data as well as from a three-dimensional chemical-climate model (MRI-CCM2). The TANSO-FTS data have high correlations with the ozonesonde data. The seasonal trends of the retrieved tropospheric ozone are consistent with those of the ozonesonde data. The spatial distribution of the tropospheric ozone from the TANSO-FTS and MRI-CCM2 shows good agreement, especially in the high-level tropospheric ozone regions. We also retrieve tropospheric H2O and HDO profiles simultaneously, accounting for the cross correlations between the water isotopes. The joint retrieval results in precise estimation of the isotope ratio by partial cancellation of systematic errors common to both H2O and HDO. The retrieved profiles and columns are compared with radiosonde, GPS, and ground-based high-resolution FTS data. The temporal and spatial variations of the precipitable water and the isotope ratio are consistent with those of the validation data. Finally, air pollutants such as CH3OH and NH3 are retrieved using the retrieved ozone and water vapor. We present the latitudinal and seasonal variations of CH3OH

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean.

PubMed

Read, Katie A; Mahajan, Anoop S; Carpenter, Lucy J; Evans, Mathew J; Faria, Bruno V E; Heard, Dwayne E; Hopkins, James R; Lee, James D; Moller, Sarah J; Lewis, Alastair C; Mendes, Luis; McQuaid, James B; Oetjen, Hilke; Saiz-Lopez, Alfonso; Pilling, Michael J; Plane, John M C

2008-06-26

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Horizonal and Vertical Spatial Patterns of Radon and Other Soil-gases Across the El Pilar Fault Trace at Guaraphiche, Edo. Surce (Venezuela)

NASA Astrophysics Data System (ADS)

LaBrecque, J. J.

2002-05-01

Soil-gases (radon, thoron, carbon dioxide and hydrogen) were measured at 63-cm depths along a transect perpendicular to the rupture (fault trace) from the 1997 Caricao earthquake (Mw=6.9) at Guarapiche, state of Sucre (Venezuela). The transect was about 40 meters long with ten sampling points with the spacings was smaller near the rupture. The shapes of the horizontal spatial patterns for radon (Rn-222), thoron (Rn-220) and total radon (Rn-222+Rn-220) were similar; the gas concentrations increased from both ends of the transect toward the rupture where a dip (valley) occurred. Both carbon dioxide and hydrogen gases showed anomalous values at the same sampling points. Twin peaks (anomalies) had been previously reported and suggested that they were due to blockage in the rupture. We have also determined soil-gases from 25-cm to 155-cm depths near the rupture and at the ends of the transect. The results showed that the soil-gas concentrations were not only higher in the upper levels (less than 65-cm) near the fault trace but were similar or greater than the lower levels. Thus, producing the twin peaks when soil-gas sampling was performed at the 65-cm depth. When the sampling was performed at only 45-cm depth the dip over the rupture was much less and the patterns looked more like a broad doublet peak. In conclusion, one can clearly see that not only positive soil-gas anomalies can occur over a fault trace but also negative ones too. 1) This work was partially funded by a research contract from the Venezuelan National Science Foundation (CONICIT Proyecto S1-95000448). 2) Mailing Address: Centro de Quimica, 8424 NW 56th Street, Suite 00204,Miami, Fl 33166 (USA). E-mail jjlabrec@ivic.ve FAX: +58-212-504-1214

Towards uncertainty estimates in global operational forecasts of trace gases in the Copernicus Atmosphere Monitoring System

NASA Astrophysics Data System (ADS)

Huijnen, V.; Bouarar, I.; Chabrillat, S. H.; Christophe, Y.; Thierno, D.; Karydis, V.; Marecal, V.; Pozzer, A.; Flemming, J.

2017-12-01

Operational atmospheric composition analyses and forecasts such as developed in the Copernicus Atmosphere Monitoring Service (CAMS) rely on modules describing emissions, chemical conversion, transport and removal processing, as well as data assimilation methods. The CAMS forecasts can be used to drive regional air quality models across the world. Critical analyses of uncertainties in any of these processes are continuously needed to advance the quality of such systems on a global scale, ranging from the surface up to the stratosphere. With regard to the atmospheric chemistry to describe the fate of trace gases, the operational system currently relies on a modified version of the CB05 chemistry scheme for the troposphere combined with the Cariolle scheme to describe stratospheric ozone, as integrated in ECMWF's Integrated Forecasting System (IFS). It is further constrained by assimilation of satellite observations of CO, O3 and NO2. As part of CAMS we have recently developed three fully independent schemes to describe the chemical conversion throughout the atmosphere. These parameterizations originate from parent model codes in MOZART, MOCAGE and a combination of TM5/BASCOE. In this contribution we evaluate the correspondence and elemental differences in the performance of the three schemes in an otherwise identical model configuration (excluding data-assimilation) against a large range of in-situ and satellite-based observations of ozone, CO, VOC's and chlorine-containing trace gases for both troposphere and stratosphere. This analysis aims to provide a measure of model uncertainty in the operational system for tracers that are not, or poorly, constrained by data assimilation. It aims also to provide guidance on the directions for further model improvement with regard to the chemical conversion module.

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

NASA Technical Reports Server (NTRS)

Cooper, David E.

1986-01-01

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Evidence for Interfacial Halogen Bonding.

PubMed

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validation of Global Climatologies of Trace Gases Using NASA Global Tropospheric Experiment (GTE) Data

NASA Technical Reports Server (NTRS)

Courchaine, Brian; Venable, Jessica C.

1995-01-01

Methane is an important trace gas because it is a greenhouse gas that affects the oxidative capacity of the atmosphere. It is produced from biological and anthropogenic sources, and is increasing globally at a rate of approximately 0.6% per year [Climate Change 1992, IPCC]. By using National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL) ground station data, a global climatology of methane values was produced. Unfortunately, because the NOAA/CMDL ground stations are so sparse, the global climatology is low resolution. In order to compensate for this low resolution data, it was compared to in-situ flight data obtained from the NASA Global Tropospheric Experiment (GTE). The smoothed ground station data correlated well with the flight data. Thus, for the first time it is shown that the smoothing process used to make global contours of methane using the ground stations is a plausible way to approximate global atmospheric concentrations of the gas. These verified climatologies can be used for testing large-scale models of chemical production, destruction, and transport. This project develops the groundwork for further research in building global climatologies from sparse ground station data and studying the transport and distribution of trace gases.

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

Measurements of Long-Lived Trace Gases from Commercial Aircraft Platforms: Development of Instrumentation

NASA Technical Reports Server (NTRS)

2002-01-01

The upper troposphere (6-12 km altitude) is a poorly understood and highly vulnerable region of the atmosphere. It is important because many trace species, including ozone, have their greatest impact as greenhouse (infrared-absorbing) gases in this region. The addition of relatively small amounts of anthropogenic chemicals, such as nitrogen oxides, can have a dramatic effect on the abundance of ozone. Some of these pollutants are deposited directly, e.g., by aircraft, while others are transported in. The primary goal of this project was to measure several chemical compounds in the upper troposphere that will help us to understand how air is to transported to that part of the atmosphere; that is, does it come down from the stratosphere, does it rise from the surface via convection, and so on. To obtain adequate sampling to accomplish this goal, we proposed to make measurements from revenue aircraft during normal flight operations.

Dating of young groundwater using four anthropogenic trace gases (SF6, SF5CF3, CFC-12 and Halon-1301): methodology and first results.

PubMed

Bartyzel, Jakub; Rozanski, Kazimierz

2016-01-01

A dedicated, GC-based analytical system is presented which allows detection of four anthropogenic trace gases (SF6, SF5CF3, CFC-12 and Halon-1301) in a single water sample, with detection limits and measurement uncertainties sufficiently low to employ them as quantitative indicators of groundwater age. The gases dissolved in water are extracted in the field using the method based on a dynamic head-space concept. In the laboratory, the investigated gases are cryogenically enriched, separated and measured using an electron capture detector. Reproducibility of the analyses is in the order of 2-5 %. The investigated tracers were measured in several production wells located in the recharge area of an intensively exploited aquifer in southern Poland. While the piston-flow ages of groundwater in the investigated wells revealed internal consistency, they appeared to be generally smaller than the ages derived from time series of tritium content in those wells, interpreted by lumped-parameter models. This difference stems mainly from significantly longer travel times of tritium through the unsaturated zone, when compared to the gaseous tracers being used. The results of this study highlight the benefits of using multiple tracing in quantifying timescales of groundwater flow in shallow aquifer systems.

Halogenated boron-dipyrromethenes: synthesis, properties and applications.

PubMed

Lakshmi, Vellanki; Rao, Malakalapalli Rajeswara; Ravikanth, Mangalampalli

2015-03-07

Boron-dipyrromethene dyes (BODIPYs) containing halogens at pyrrole carbons are very useful synthons for the synthesis of a variety of BOIDPYs for a wide range of applications. Among the functional groups, halogens are the functional groups which can be regiospecifically introduced at any desired pyrrole carbon of the BODIPY framework by adopting appropriate synthetic strategies. The halogenated BODIPYs can undergo facile nucleophilic substitution reactions to prepare several interesting BODIPY based compounds. This review describes the synthesis, properties and potential applications of halogenated BODIPYs containing one to six halogens at the pyrrole carbons of the BODIPY core as well as properties and applications of some of the substituted BODIPYs derived from halogenated BODIPYs.

Intrinsic Chemiluminescence Generation during Advanced Oxidation of Persistent Halogenated Aromatic Carcinogens.

PubMed

Mao, Li; Liu, Yu-Xiang; Huang, Chun-Hua; Gao, Hui-Ying; Kalyanaraman, Balaraman; Zhu, Ben-Zhan

2015-07-07

The ubiquitous distribution coupled with their carcinogenicity has raised public concerns on the potential risks to both human health and the ecosystem posed by the halogenated aromatic compounds (XAr). Recently, advanced oxidation processes (AOPs) have been increasingly favored as an "environmentally-green" technology for the remediation of such recalcitrant and highly toxic XAr. Here, we show that AOPs-mediated degradation of the priority pollutant pentachlorophenol and all other XAr produces an intrinsic chemiluminescence that directly depends on the generation of the extremely reactive hydroxyl radicals. We propose that the hydroxyl radical-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual chemiluminescence production. A rapid, sensitive, simple, and effective chemiluminescence method was developed to quantify trace amounts of XAr and monitor their real-time degradation kinetics. These findings may have broad biological and environmental implications for future research on this important class of halogenated persistent organic pollutants.

Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

NASA Astrophysics Data System (ADS)

Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

2011-12-01

Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

Relative effects on stratospheric ozone of halogenated methanes and ethanes of social and industrial interest

NASA Technical Reports Server (NTRS)

Fisher, Donald A.; Hales, Charles H.; Filkin, David L.; Ko, Malcolm K. W.; Sze, N. Dak; Connell, Peter S.; Wuebbles, Donald J.; Isaksen, Ivar S. A.; Stordal, Frode

1990-01-01

Four atmospheric modeling groups have calculated relative effects of several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a, carbon tetrachloride; and methyl chloroform) on stratospheric ozone. Effects on stratospheric ozone were calculated for each compound and normalized relative to the effect of CFC-11. These models include the representations for homogeneous physical and chemical processes in the middle atmosphere but do no account for either heterogeneous chemistry or polar dynamics which are important in the spring time loss of ozone over Antarctica. Relative calculated effects using a range of models compare reasonably well. Within the limits of the uncertainties of these model results, compounds now under consideration as functional replacements for fully halogenated compounds have modeled stratospheric ozone reductions of 10 percent or less of that of CFC-11. Sensitivity analyses examined the sensitivity of relative calculated effects to levels of other trace gases, assumed transport in the models, and latitudinal and seasonal local dependencies. Relative effects on polar ozone are discussed in the context of evolving information on the special processes affecting ozone, especially during polar winter-springtime. Lastly, the time dependency of relative effects were calculated.

Volatile halogenated hydrocarbons over the western Pacific between 43° and 4°N

NASA Astrophysics Data System (ADS)

Quack, Birgit; Suess, Erwin

1999-01-01

A spectrum of halogenated hydrocarbon compounds in marine air masses were surveyed over an area in the western Pacific between 43°N, 150°E and 4°N, 113°E in September 1994. The ship's track between northern Japan and Singapore traversed three climatic zones of the northern hemisphere. Recently polluted air, clean marine air derived from the central Pacific Ocean from different latitudes, and marine air from the Indonesian archipelago were collected. Tetrachloroethene and trichloroethene of anthropogenic origin, brominated halocarbons as tribromomethane, dibromochloromethane and bromodichloromethane of anthropogenic and natural sources, and other trace gases were measured in the air samples. Very sparse data on the distribution of these compounds exist for the western Pacific atmosphere. The distribution patterns of the compounds were related to synoptic-scale meteorology, spatial conditions, and origin of the air masses. Anthropogenic and natural sources for both chlorinated and brominated substances were identified. Tetrachloroethene and trichloroethene concentrations and their ratios identify anthropogenic sources. Their mixing ratios were quite low compared to previously published data. They are in agreement with expected low concentrations of photochemically active substances during autumn, with an overall decrease in concentrations toward lower latitudes, and with a decrease of emissions during recent years. Strong evidence for a natural source of trichloroethene was discovered in the tropical region. The concentrations of naturally released brominated species were high compared to other measurements over the Pacific. Gradients toward the coasts and elevated concentrations in air masses influenced by coastal emissions point to significant coastal sources of these compounds. The trace gas composition of anthropogenic and natural compounds clearly identified the air masses which were traversed during the cruise.

Halogen bonding in solution: thermodynamics and applications.

PubMed

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

Biomass burning and the production of greenhouse gases

NASA Technical Reports Server (NTRS)

Levine, Joel S.

1991-01-01

The present discussion of related aspects of biomass burning describes a technique for estimating the instantaneous emission of trace gases generated by such fires on the basis of satellite imagery, and notes that burning results in significantly enhanced biogenic emissions of N2O, NO, and CH4. Biomass burning therefore has both immediate and long-term impacts on the trace-gas content of the atmosphere. The effects of Kuwait's oil fires, which encompass both combustion gases and particulates, are compared with those of the more general problem.

Community Radiative Transfer Model Applications - A Study of the Retrieval of Trace Gases in the Atmosphere from Cross-track Infrared Sounder (CrIS) Data of a Full-spectral Resolution

NASA Astrophysics Data System (ADS)

Liu, Q.; Nalli, N. R.; Tan, C.; Zhang, K.; Iturbide, F.; Wilson, M.; Zhou, L.

2015-12-01

The Community Radiative Transfer Model (CRTM) [3] operationally supports satellite radiance assimilation for weather forecasting, sensor data verification, and the retrievals of satellite products. The CRTM has been applied to UV and visible sensors, infrared and microwave sensors. The paper will demonstrate the applications of the CRTM, in particular radiative transfer in the retrieva algorithm. The NOAA Unique CrIS/ATMS Processing System (NUCAPS) operationally generates vertical profiles of atmospheric temperature (AVTP) and moisture (AVMP) from Suomi NPP Cross-track Infrared Sounder (CrIS) and Advanced Technology Microwave Sounder (ATMS) measurements. Current operational CrIS data have reduced spectral resolution: 1.25 cm-1 for a middle wave band and 2.5 cm-1 for a short-wave wave band [1]. The reduced spectral data largely degraded the retrieval accuracy of trace gases. CrIS full spectral data are also available now which have single spectral resolution of 0.625 cm-1 for all of the three bands: long-wave band, middle wave band, and short-wave band. The CrIS full-spectral resolution data is critical to the retrieval of trace gases such as O3, CO [2], CO2, and CH4. In this paper, we use the Community Radiative Transfer Model (CRTM) to study the impact of the CrIS spectral resolution on the retrieval accuracy of trace gases. The newly released CRTM version 2.2.1 can simulates Hamming-apodized CrIS radiance of a full-spectral resolution. We developed a small utility that can convert the CRTM simulated radiance to un-apodized radiance. The latter has better spectral information which can be helpful to the retrievals of the trace gases. The retrievals will be validated using both NWP model data as well as the data collected during AEROSE expeditions [4]. We will also discuss the sensitivity on trace gases between apodized and un-apodized radiances. References[1] Gambacorta, A., et al.(2013), IEEE Lett., 11(9), doi:10.1109/LGRS.2014.230364, 1639-1643. [2] Han, Y., et

Adsorption of halogens on metal surfaces

NASA Astrophysics Data System (ADS)

Andryushechkin, B. V.; Pavlova, T. V.; Eltsov, K. N.

2018-06-01

This paper presents a review of the experimental and theoretical investigations of halogen interaction with metal surfaces. The emphasis was placed on the recent measurements performed with a scanning tunneling microscope in combination with density functional theory calculations. The surface structures formed on metal surface after halogen interaction are classified into three groups: chemisorbed monolayer, surface halide, bulk-like halide. Formation of monolayer structures is described in terms of surface phase transitions. Surface halide phases are considered to be intermediates between chemisorbed halogen and bulk halide. The modern theoretical approaches in studying the dynamics of metal halogenation reactions are also presented.

Halogenated solvent remediation

DOEpatents

Sorenson, Kent S.

2004-08-31

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

Transport of Asian Aerosols and Trace Gases to North America During the INTEX-B Field Campaign: A Regional Chemical Transport Model Analysis.

NASA Astrophysics Data System (ADS)

Adhikary, B.; Kulkarni, S.; Carmichael, G. R.; Tang, Y.; Dallura, A.; Mena, M.; Streets, D.; Zhang, Q.

2007-12-01

The Intercontinental Chemical Transport Experiment-Phase B (INTEX-B) was conducted over the Pacific Ocean during the 2006 North American spring season. One of the scientific objectives of the INTEX-B field campaign was to quantify the transport and chemical evolution/aging of Asian air pollution into North America. The field campaign deployed multiple experimental platforms such as satellites, aircrafts and surface measurements stations to study the pollution outflow to North America. Three dimensional chemical transport models were used to provide chemical weather forecasts and assist in flight planning during the mission. The Sulfur Transport and dEposition Model (STEM) is a regional chemical transport model developed at the University of Iowa. The STEM model was involved in providing chemical weather forecasts and assist in flight planning during the INTEX-B intensive field campaign. In this study we will report the STEM model performance of aerosols and trace gases in its ability to capture the pollutant plume with experimental observations obtained from the field campaign. The study will then relate the emissions of trace gases and aerosols to atmospheric composition, sources and sinks using the newly developed emissions inventory for the INTEX-B field campaign.

What’s New in Enzymatic Halogenations

PubMed Central

Fujimori, Danica Galoniæ; Walsh, Christopher T.

2007-01-01

Summary The halogenation of thousands of natural products occurs during biosynthesis and often confers important functional properties. While haloperoxidases had been the default paradigm for enzymatic incorporation of halogens, via X+ equivalents into organic scaffolds, a combination of microbial genome sequencing, enzymatic studies and structural biology have provided deep new insights into enzymatic transfer of halide equivalents in three oxidation states. These are: (1) the halide ions (X−) abundant in nature, (2) halogen atoms (X•), and (3) the X+ equivalents. The mechanism of halogen incorporation is tailored to the electronic demands of specific substrates and involves enzymes with distinct redox coenzyme requirements. PMID:17881282

Halogenated arsenenes as Dirac materials

NASA Astrophysics Data System (ADS)

Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

2016-07-01

Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155-3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

Using the full IASI spectrum for the physical retrieval of temperature, H2O, HDO, O3, minor and trace gases

NASA Astrophysics Data System (ADS)

Serio, C.; Blasi, M. G.; Liuzzi, G.; Masiello, G.; Venafra, S.

2017-02-01

IASI (Infrared Atmospheric Sounder Interferometer) is flying on the European MetOp series of weather satellites. Besides acquiring temperature and humidity data, IASI also observes the infrared emission of the main minor and trace atmospheric components with high precision. The retrieval of these gases would be highly beneficial to the efforts of scientists monitoring Earths climate. IASI retrieval capability and algorithms have been mostly driven by Numerical Weather Prediction centers, whose limited resources for data transmission and computing is hampering the full exploitation of IASI information content. The quest for real or nearly real time processing has affected the precision of the estimation of minor and trace gases, which are normally retrieved on a very coarse spatial grid. The paper presents the very first retrieval of the complete suite of IASI target parameters by exploiting all its 8461 channels. The analysis has been exemplified for sea surface and the target parameters will include sea surface temperature, temperature profile, water vapour and HDO profiles, ozone profile, total column amount of CO, CO2, CH4, N2O, SO2, HNO3, NH3, OCS and CF4. Concerning CO2, CH4 and N2O, it will be shown that their colum amount can be obtained for each single IASI IFOV (Instantaneous Field of View) with a precision better than 1-2%, which opens the possibility to analyze, e.g., the formation of regional patterns of greenhouse gases. To assess the quality of the retrieval, a case study has been set up which considers two years of IASI soundings over the Hawaii, Manua Loa validation station.

Metal halogen battery construction with improved technique for producing halogen hydrate

DOEpatents

Fong, Walter L.; Catherino, Henry A.; Kotch, Richard J.

1983-01-01

An improved electrical energy storage system comprising, at least one cell having a positive electrode and a negative electrode separated by aqueous electrolyte, a store means wherein halogen hydrate is formed and stored as part of an aqueous material having a liquid level near the upper part of the store, means for circulating electrolyte through the cell, conduit means for transmitting halogen gas formed in the cell to a hydrate forming apparatus associated with the store, said hydrate forming apparatus including, a pump to which there is introduced quantities of the halogen gas and chilled water, said pump being located in the store and an outlet conduit leading from the pump and being substantially straight and generally vertically disposed and having an exit discharge into the gas space above the liquid level in the store, and wherein said hydrate forming apparatus is highly efficient and very resistant to plugging or jamming. The disclosure also relates to an improved method for producing chlorine hydrate in zinc chlorine batteries.

Devices and methods to detect and quantify trace gases

DOEpatents

Allendorf, Mark D.; Robinson, Alex

2016-05-03

Sensing devices based on a surface acoustic wave ("SAW") device coated with an absorbent crystalline or amorphous layer for detecting at least one chemical analyte in a gaseous carrier. Methods for detecting the presence of a chemical analyte in a gaseous carrier using such devices are also disclosed. The sensing devices and methods for their use may be configured for sensing chemical analytes selected from the group consisting of water vapor, carbon dioxide, methanol, ethanol, carbon monoxide, nitric oxide, nitrous oxide, organic amines, organic compounds containing NO.sub.2 groups, halogenated hydrocarbons, acetone, hexane, toluene, isopropanol, alcohols, alkanes, alkenes, benzene, functionalized aromatics, ammonia (NH.sub.3), phosgene (COCl.sub.2), sulfur mustard, nerve agents, sulfur dioxide, tetrahydrofuran (THF) and methyltertbutyl ether (MTBE) and combinations thereof.

Halogenated compounds from marine algae.

PubMed

Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

2010-08-09

Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds.

Halogenated Compounds from Marine Algae

PubMed Central

Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

2010-01-01

Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds. PMID:20948909

Structural Perspective on Enzymatic Halogenation

PubMed Central

2008-01-01

Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% (HarrisC. M.; KannanR.; KopeckaH.; HarrisT. M.J. Am. Chem. Soc.1985, 107, 6652−6658). This Account analyzes how structure underlies mechanism in halogenases, the molecular machines designed by nature to incorporate halogens into diverse substrates. Traditional synthetic methods of integrating halogens into complex molecules are often complicated by a lack of specificity and regioselectivity. Nature, however, has developed a variety of elegant mechanisms for halogenating specific substrates with both regio- and stereoselectivity. An improved understanding of the biological routes toward halogenation could lead to the development of novel synthetic methods for the creation of new compounds with enhanced functions. Already, researchers have co-opted a fluorinase from the microorganism Streptomyces cattleya to produce 18F-labeled molecules for use in positron emission tomography (PET) (DengH.; CobbS. L.; GeeA. D.; LockhartA.; MartarelloL.; McGlincheyR. P.; O’HaganD.; OnegaM.Chem. Commun.2006, 652−654). Therefore, the discovery and characterization of naturally occurring enzymatic halogenation mechanisms has become an active area of research. The catalogue of known halogenating enzymes has expanded from the familiar haloperoxidases to include oxygen-dependent enzymes and fluorinases. Recently, the discovery of a nucleophilic halogenase that catalyzes chlorinations has expanded the repertoire of biological halogenation chemistry (DongC.; HuangF.; DengH.; SchaffrathC.; SpencerJ. B.; O’HaganD.; NaismithJ. H.Nature2004, 427, 561−56514765200). Structural characterization has provided a basis toward a mechanistic understanding of the specificity

Independent Evolution of Six Families of Halogenating Enzymes.

PubMed

Xu, Gangming; Wang, Bin-Gui

2016-01-01

Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

Independent Evolution of Six Families of Halogenating Enzymes

PubMed Central

Xu, Gangming; Wang, Bin-Gui

2016-01-01

Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity. PMID:27153321

Process for removal of ammonia and acid gases from contaminated waters

DOEpatents

King, C. Judson; MacKenzie, Patricia D.

1985-01-01

Contaminating basic gases, i.e., ammonia, and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with steam, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

Process for removal of ammonia and acid gases from contaminated waters

DOEpatents

King, C.J.; Mackenzie, P.D.

1982-09-03

Contaminating basic gases, i.e., ammonia and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with stream, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

Compositional variation in aging volcanic plumes - Analysis of gaseous SO2, CO2 and halogen species in volcanic emissions using an Unmanned Aerial Vehicle (UAV).

NASA Astrophysics Data System (ADS)

Rüdiger, Julian; Lukas, Tirpitz; Bobrowski, Nicole; Gutmann, Alexandra; Liotta, Marcello; de Moor, Maarten; Hoffmann, Thorsten

2017-04-01

Volcanoes are a large source for several reactive atmospheric trace gases including sulfur and halogen containing species. The detailed understanding of volcanic plume chemistry is needed to draw information from gas measurements on subsurface processes. This knowledge is essential for using gas measurements as a monitoring tool for volcanic activity. The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable from safe distance by spectroscopic remote sensing techniques. BrO is not directly emitted, but is formed in the plume by a multiphase reaction mechanism. The abundance of BrO changes as a function of the distance from the vent as well as the spatial position in the plume. The precursor substance for the formation of BrO is HBr with Br2as an intermediate product. In this study we present the application of a UAV as a carrier for a remote-controlled sampling system for halogen species (Br2, HBr, BrCl, etc), based on the gas diffusion denuder technique, which allows speciation and enrichment by selective organic reactions. For the analysis of gaseous SO2 and CO2 an in-situ gas monitoring system was additionally mounted. This setup was deployed into the gas plumes of Stromboli Volcano (Italy), Masaya Volcano (Nicaragua) and Turrialba Volcano (Costa Rica) in 2016, to investigate the halogen chemistry at distant locations in the plume further downwind to the emission source, which are in most cases not accessible by other approaches. Flights into the plume were conducted with ascents of up to 1000 m. From telemetrically transmitted SO2 mixing ratios, areas of dense plume where localized to keep the UAV stationary for up to 10 minutes of sampling time. Additionally, ground based samples were taken at the crater rim (at Masaya and Turrialba) using alkaline traps, denuder and gas sensors for comparison with airborne-collected data. Herein we will present time and spatial resolved gas mixing ratio

Halogen-bonding-triggered supramolecular gel formation

NASA Astrophysics Data System (ADS)

Meazza, Lorenzo; Foster, Jonathan A.; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W.

2013-01-01

Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

Trace Gases and Aerosol Optical Properties Over the US Mid-Atlantic During Summer 2001

NASA Astrophysics Data System (ADS)

Doddridge, B. G.; Piety, C. A.

2001-12-01

Anthropogenic emissions from rapid urban sprawl, commuter/commercial traffic and industrialization along the East Coast of the United States have a profound effect on urban and regional air quality. During summer 2001 we used a light aircraft research platform operated from North Carolina northward through Pennsylvania measuring meteorological scalars, selected trace gases and aerosol optical properties on selected pollution episode days. The goal of this research is to gain an improved understanding of the sources, sinks, transport and photochemical transformations controlling the observed abundance of photochemical oxidants and fine particulate haze over the U.S. Mid-Atlantic region. The aircraft research capabilities will be described, over 60 research flights totaling in excess of 160 flight hours summarized, and key findings presented. Although westerly transport of remnant ozone and haze along with precursors can make substantial contributions to observed urban corridor air quality aloft, significant production downwind of the urban center often can occur within the planetary boundary layer during the afternoon hours.

Trapping, chemistry, and export of trace gases in the South Asian summer monsoon observed during CARIBIC flights in 2008

NASA Astrophysics Data System (ADS)

Rauthe-Schöch, Armin; Baker, Angela K.; Schuck, Tanja J.; Brenninkmeijer, Carl A. M.; Zahn, Andreas; Hermann, Markus; Stratmann, Greta; Ziereis, Helmut; van Velthoven, Peter F. J.; Lelieveld, Jos

2016-03-01

The CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) passenger aircraft observatory performed in situ measurements at 10-12 km altitude in the South Asian summer monsoon anticyclone between June and September 2008. These measurements enable us to investigate this atmospheric region (which so far has mostly been observed from satellites) using the broad suite of trace gases and aerosol particles measured by CARIBIC. Elevated levels of a variety of atmospheric pollutants (e.g. carbon monoxide, total reactive nitrogen oxides, aerosol particles, and several volatile organic compounds) were recorded. The measurements provide detailed information about the chemical composition of air in different parts of the monsoon anticyclone, particularly of ozone precursors. While covering a range of 3500 km inside the monsoon anticyclone, CARIBIC observations show remarkable consistency, i.e. with distinct latitudinal patterns of trace gases during the entire monsoon period. Using the CARIBIC trace gas and aerosol particle measurements in combination with the Lagrangian particle dispersion model FLEXPART, we investigated the characteristics of monsoon outflow and the chemical evolution of air masses during transport. The trajectory calculations indicate that these air masses originated mainly from South Asia and mainland Southeast Asia. Estimated photochemical ages of the air were found to agree well with transport times from a source region east of 90-95° E. The photochemical ages of the air in the southern part of the monsoon anticyclone were systematically younger (less than 7 days) and the air masses were mostly in an ozone-forming chemical mode. In its northern part the air masses were older (up to 13 days) and had unclear ozone formation or destruction potential. Based on analysis of forward trajectories, several receptor regions were identified. In addition to predominantly westward transport, we found evidence for

Trapping, chemistry and export of trace gases in the South Asian summer monsoon observed during CARIBIC flights in 2008

NASA Astrophysics Data System (ADS)

Rauthe-Schöch, A.; Baker, A. K.; Schuck, T. J.; Brenninkmeijer, C. A. M.; Zahn, A.; Hermann, M.; Stratmann, G.; Ziereis, H.; van Velthoven, P. F. J.; Lelieveld, J.

2015-03-01

The CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) passenger aircraft observatory performed in situ measurements at 10-12 km altitude in the South Asian summer monsoon anticyclone between June and September 2008. These measurements enable us to investigate this atmospheric region, which so far has mostly been observed from satellites, using the broad suite of trace gases and aerosols measured by CARIBIC. Elevated levels of a range of atmospheric pollutants were recorded e.g. carbon monoxide, total reactive nitrogen oxides, aerosol particles and several volatile organic compounds. The measurements provide detailed information about the chemical composition of air in different parts of the monsoon anticyclone, particularly of ozone precursors. While covering a range of 3500 km inside the monsoon anticyclone, CARIBIC observations show remarkable consistency, i.e. with regular latitudinal patterns of trace gases during the entire monsoon period. Trajectory calculations indicate that these air masses originated mainly from South Asia and Mainland Southeast Asia. Using the CARIBIC trace gas and aerosol measurements in combination with the Lagrangian particle dispersion model FLEXPART we investigated the characteristics of monsoon outflow and the chemical evolution of air masses during transport. Estimated photochemical ages of the air were found to agree well with transport times from a source region east of 95° E. The photochemical ages of the air in the southern part of the monsoon anticyclone were consistently younger (less than 7 days) and the air masses mostly in an ozone forming chemical regime. In its northern part the air masses were older (up to 13 days) and had unclear ozone formation or destruction potential. Based on analysis of forward trajectories several receptor regions were identified. In addition to predominantly westward transport, we found evidence for efficient transport (within 10 days) to

Treatment System for Removing Halogenated Compounds from Contaminated Sources

NASA Technical Reports Server (NTRS)

Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor); Quinn, Jacqueline W. (Inventor)

2015-01-01

A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

Passivation of quartz for halogen-containing light sources

DOEpatents

Falkenstein, Zoran

1999-01-01

Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

DOEpatents

Frazer, J.W.

1959-08-18

A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

Real-time measurement and control of waste anesthetic gases during veterinary surgeries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burkhart, J.E.; Stobbe, T.J.

1990-12-01

Veterinary clinics are typically small businesses without access to sophisticated occupational safety and health programs that may exist for larger firms or hospitals. Exposures to waste anesthetic gases have been linked to a myriad of adverse health-related conditions. Excessive exposures to anesthetic agents are possible because many of the clinics use portable gas delivery carts that are not designed to capture waste gases. While scavenging systems are available to remove waste anesthetic gases, the cost may be prohibitive for smaller clinics and the effectiveness of these systems has not been fully established in veterinary clinics. The National Institute for Occupationalmore » Safety and Health (NIOSH) recommends limiting exposures to nitrous oxide (N2O) to a time-weighted average (TWA) concentration of 25 ppm and halogenated agents to 2 ppm. The NIOSH TWA is based on the weight of the agent collected from a 45-L air sample by charcoal adsorption over a sampling period not to exceed 1 hr. The NIOSH criteria state that, in most situations, control of N2O to the TWA as defined will result in levels of approximately 0.5 ppm of the halogenated agent. At present, no Occupational Safety and Health Administration (OSHA) permissible exposure level (PEL) exists for exposure to anesthetic agents; nor do specific recommendations exist for veterinary scavenging systems. Waste anesthetic gas exposures were determined using a modified MIRAN 1A at five veterinary clinics operating within the Morgantown, West Virginia, vicinity. For unscavenged systems of methoxyflurane and halothane, 1-hr time-weighted average exposures ranged from 0.5 to 45.5 ppm and 0.2 to 105.4 ppm, respectively.« less

Dynamics of submarine groundwater discharge and associated fluxes of dissolved nutrients, carbon, and trace gases to the coastal zone (Okatee River estuary, South Carolina)

USGS Publications Warehouse

Porubsky, W.P.; Weston, N.B.; Moore, W.S.; Ruppel, C.; Joye, S.B.

2014-01-01

Multiple techniques, including thermal infrared aerial remote sensing, geophysical and geological data, geochemical characterization and radium isotopes, were used to evaluate the role of groundwater as a source of dissolved nutrients, carbon, and trace gases to the Okatee River estuary, South Carolina. Thermal infrared aerial remote sensing surveys illustrated the presence of multiple submarine groundwater discharge sites in Okatee headwaters. Significant relationships were observed between groundwater geochemical constituents and 226Ra activity in groundwater with higher 226Ra activity correlated to higher concentrations of organics, dissolved inorganic carbon, nutrients, and trace gases to the Okatee system. A system-level radium mass balance confirmed a substantial submarine groundwater discharge contribution of these constituents to the Okatee River. Diffusive benthic flux measurements and potential denitrification rate assays tracked the fate of constituents in creek bank sediments. Diffusive benthic fluxes were substantially lower than calculated radium-based submarine groundwater discharge inputs, showing that advection of groundwater-derived nutrients dominated fluxes in the system. While a considerable potential for denitrification in tidal creek bank sediments was noted, in situ denitrification rates were nitrate-limited, making intertidal sediments an inefficient nitrogen sink in this system. Groundwater geochemical data indicated significant differences in groundwater chemical composition and radium activity ratios between the eastern and western sides of the river; these likely arose from the distinct hydrological regimes observed in each area. Groundwater from the western side of the Okatee headwaters was characterized by higher concentrations of dissolved organic and inorganic carbon, dissolved organic nitrogen, inorganic nutrients and reduced metabolites and trace gases, i.e. methane and nitrous oxide, than groundwater from the eastern side

Experimental and computational evidence of halogen bonds involving astatine

NASA Astrophysics Data System (ADS)

Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

2018-03-01

The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

NASA Astrophysics Data System (ADS)

Oliveira, Vytor; Cremer, Dieter

2017-08-01

Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

Active and widespread halogen chemistry in the tropical and subtropical free troposphere

DOE PAGES

Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil; ...

2015-06-29

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O 3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O 3 and methane (CH 4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric Omore » 3. The observed BrO concentrations increase strongly with altitude (~3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Br y), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. Lastly, the halogen-catalyzed loss of tropospheric O 3 needs to be considered when estimating past and future ozone radiative effects.« less

Active and widespread halogen chemistry in the tropical and subtropical free troposphere

PubMed Central

Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil; Coburn, Sean; Dix, Barbara; Koenig, Theodore K.; Apel, Eric; Bowdalo, Dene; Campos, Teresa L.; Eloranta, Ed; Evans, Mathew J.; DiGangi, Joshua P.; Zondlo, Mark A.; Gao, Ru-Shan; Haggerty, Julie A.; Hall, Samuel R.; Hornbrook, Rebecca S.; Jacob, Daniel; Morley, Bruce; Pierce, Bradley; Reeves, Mike; Romashkin, Pavel; ter Schure, Arnout; Volkamer, Rainer

2015-01-01

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects. PMID:26124148

Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere

NASA Technical Reports Server (NTRS)

Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil; Coburn, Sean; Dix, Barbara; Koenig, Theodore K.; Apel, Eric; Bowdalo, Dene; Campos, Teresa; Eloranta, Ed;

Active and widespread halogen chemistry in the tropical and subtropical free troposphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O 3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O 3 and methane (CH 4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric Omore » 3. The observed BrO concentrations increase strongly with altitude (~3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Br y), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. Lastly, the halogen-catalyzed loss of tropospheric O 3 needs to be considered when estimating past and future ozone radiative effects.« less

Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

PubMed

Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

2017-03-21

During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

The halogen bond: Nature and applications

NASA Astrophysics Data System (ADS)

Costa, Paulo J.

2017-10-01

The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

Magnesium Bisamide-Mediated Halogen Dance of Bromothiophenes.

PubMed

Yamane, Yoshiki; Sunahara, Kazuhiro; Okano, Kentaro; Mori, Atsunori

2018-03-16

A magnesium bisamide-mediated halogen dance of bromothiophenes is described. The thienylmagnesium species generated in situ is more stable than the corresponding thienyllithium species, which was applied to trap the transient anion species with several electrophiles, such as allyl iodide, phenyl isocyanate, and tributylstannyl chloride. The utility of the magnesium bisamide-mediated halogen dance is useful in the concise synthesis of a medicinally advantageous compound via a one-pot, ester-directed halogen dance/Negishi cross coupling.

Hydrogen bond and halogen bond inside the carbon nanotube

NASA Astrophysics Data System (ADS)

Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

2011-02-01

The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

PubMed

Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

2017-04-26

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

The airborne Laser Absorption Spectrometer - A new instrument of remote measurement of atmospheric trace gases

NASA Technical Reports Server (NTRS)

Shumate, M. S.; Menzies, R. T.

1978-01-01

The Laser Absorption Spectrometer is a portable instrument developed by JPL for remote measurement of trace gases from an aircraft platform. It contains two carbon dioxide lasers, two optical heterodyne receivers, appropriate optics to aim the lasers at the ground and detect the backscattered energy, and signal processing and recording electronics. Operating in the differential-absorption mode, it is possible to monitor one atmospheric gas at a time and record the data in real time. The system can presently measure ozone, ethylene, water vapor, and chlorofluoromethanes with high sensitivity. Airborne measurements were made in early 1977 from the NASA/JPL twin-engine Beechcraft and in May 1977 from the NASA Convair 990 during the ASSESS-II Shuttle Simulation Study. These flights resulted in measurements of ozone concentrations in the lower troposphere which were compared with ground-based values provided by the Air Pollution Control District. This paper describes the details of the instrument and results of the airborne measurements.

Recent developments in high altitude aircraft sampling - Mount St. Helens and stratospheric trace gases

NASA Astrophysics Data System (ADS)

Leifer, R.; Sommers, K. G.; Guggenheim, S. F.; Fisenne, I.

1981-02-01

An ultra-clean, low volume gas sampling system (CLASS), flown aboard a high altitude aircraft (WB-57F), and providing information on stratospheric trace gases is presented. Attention is given to the instrument design and the electronic control design. Since remote operation is mandatory on the WB-57F, a servo pressure transducer, electrical pressure switch for automatic shutdown, and a mechanical safety relief valve were installed on the sampling manifold, indicated on the CLASS flow chart. The electronic control system consists of hermetically sealed solid state timers, relays, and a stepping switch, for controlling the compressor pump and solenoid valves. In designing the automatic control system, vibration, shock, acceleration, extreme low temperature, and aircraft safety were important considerations. CLASS was tested on three separate occasions, and tables of analytical data from these flights are presented. Readiness capability was demonstrated when the Mount St. Helens eruption plume of May 18, 1980, was intercepted, and it was concluded that no large injection of Rn-222 entered the stratosphere or troposphere from the eruption.

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, H.S.; Sather, N.F.

1987-08-21

A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Trace analysis of impurities in bulk gases by gas chromatography-pulsed discharge helium ionization detection with "heart-cutting" technique.

PubMed

Weijun, Yao

2007-10-12

A method has been developed for the detection of low-nL/L-level impurities in bulk gases such as H(2), O(2), Ar, N(2), He, methane, ethylene and propylene, respectively. The solution presented here is based upon gas chromatography-pulsed discharge helium ionization detection (GC-PDHID) coupled with three two-position valves, one two-way solenoid valve and four packed columns. During the operation, the moisture and heavy compounds are first back-flushed via a pre-column. Then the trace impurities (except CO(2) which is diverted to a separate analytical column for separation and detection) together with the matrix enter onto a main column, followed by the heart-cut of the impurities onto a longer analytical column for complete separation. Finally the detection is performed by PDHID. This method has been applied to different bulk gases and the applicability of detecting impurities in H(2), Ar, and N(2) are herewith demonstrated. As an example, the resulting detection limit of 100 nL/L and a dynamic range of 100-1000 nL/L have been obtained using an Ar sample containing methane.

Biological cycling of atmospheric trace gases

NASA Technical Reports Server (NTRS)

Hitchcock, D. R.; Wechsler, A. E.

1972-01-01

A detailed critical review was conducted of present knowledge of the influence of biological processes on the cycling of selected atmospheric gas constituents--methane, carbon monoxide, and gaseous compounds of nitrogen (nitrous oxide, ammonia, nitric oxide, and nitrogen dioxide) and sulfur (hydrogen sulfide and sulfur dioxide). The identification was included of biological and other sources of each gas, a survey of abundance measurements reported in the literature, and a review of the atmospheric fate of each contituent. Information is provided on which to base conclusions regarding the importance of biological processes on the atmospheric distribution and surface-atmosphere exchange of each constituent, and a basis for estimating the adequacy of present knowledge of these factors. A preliminary analysis was conducted of the feasibility of monitoring the biologically influenced temporal and spatial variations in abundance of these gases in the atmosphere from satellites.

Isothermal absorption of soluble gases by atmospheric nanoaerosols

NASA Astrophysics Data System (ADS)

Elperin, T.; Fominykh, A.; Krasovitov, B.; Lushnikov, A.

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO2), dinitrogen trioxide (N2O3), and chlorine (Cl2) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

Isothermal absorption of soluble gases by atmospheric nanoaerosols.

PubMed

Elperin, T; Fominykh, A; Krasovitov, B; Lushnikov, A

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO(2)), dinitrogen trioxide (N(2)O(3)), and chlorine (Cl(2)) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

Tannins and Tannin-Related Derivatives Enhance the (Pseudo-)Halogenating Activity of Lactoperoxidase.

PubMed

Gau, Jana; Prévost, Martine; Van Antwerpen, Pierre; Sarosi, Menyhárt-Botond; Rodewald, Steffen; Arnhold, Jürgen; Flemmig, Jörg

2017-05-26

Several hydrolyzable tannins, proanthocyanidins, tannin derivatives, and a tannin-rich plant extract of tormentil rhizome were tested for their potential to regenerate the (pseudo-)halogenating activity, i.e., the oxidation of SCN - to hypothiocyanite - OSCN, of lactoperoxidase (LPO) after hydrogen peroxide-mediated enzyme inactivation. Measurements were performed using 5-thio-2-nitrobenzoic acid in the presence of tannins and related substances in order to determine kinetic parameters and to trace the LPO-mediated - OSCN formation. The results were combined with docking studies and molecular orbital analysis. The - OSCN-regenerating effect of tannin derivatives relates well with their binding properties toward LPO as well as their occupied molecular orbitals. Especially simple compounds like ellagic acid or methyl gallate and the complex plant extract were found as potent enzyme-regenerating compounds. As the (pseudo-)halogenating activity of LPO contributes to the maintenance of oral bacterial homeostasis, the results provide new insights into the antibacterial mode of action of tannins and related compounds. Furthermore, chemical properties of the tested compounds that are important for efficient enzyme-substrate interaction and regeneration of the - OSCN formation by LPO were identified.

Development of 2-D-MAX-DOAS and retrievals of trace gases and aerosols optical properties

NASA Astrophysics Data System (ADS)

Ortega, Ivan

Air pollution is a major problem worldwide that adversely a_ects human health, impacts ecosystems and climate. In the atmosphere, there are hundreds of important compounds participating in complex atmospheric reactions linked to air quality and climate. Aerosols are relevant because they modify the radiation balance, a_ect clouds, and thus Earth albedo. The amount of aerosol is often characterized by the vertical integral through the entire height of the atmosphere of the logarithm fraction of incident light that is extinguished called Aerosol Optical Depth (AOD). The AOD at 550 nm (AOD550) over land is 0.19 (multi annual global mean), and that over oceans is 0.13. About 43 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions, sample spatial scales that resemble satellite ground-pixels and atmospheric models, and help integrate remote sensing and in-situ observations to obtain optical closure on the effects of aerosols and trace gases in our changing environment. In this work, I present the recent development of the University of Colorado two dimensional (2-D) Multi-AXis Differential Optical Absorption Spectroscopy (2-D-MAX-DOAS) instrument to measure the azimuth and altitude distribution of trace gases and aerosol optical properties simultaneously with a single instrument. The instrument measures solar scattered light from any direction in the sky, including direct sun light in the hyperspectral domain. In Chapter 2, I describe the capabilities of 2-D measurements in the context of retrievals of azimuth distributions of nitrogen dioxide (NO2), formaldehyde (HCHO), and glyoxal (CHOCHO), which are precursors for tropospheric O3 and aerosols. The measurements were carried out during the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) campaign in Mainz, Germany and show the ability to bridge spatial scales to

Method for monitoring stack gases for uranium activity

DOEpatents

Beverly, C.R.; Ernstberger, E.G.

1985-07-03

A method for monitoring the stack gases of a purge cascade of gaseous diffusion plant for uranium activity. A sample stream is taken from the stack gases and contacted with a volume of moisture-laden air for converting trace levels of uranium hexafluoride, if any, in the stack gases into particulate uranyl fluoride. A continuous strip of filter paper from a supply roll is passed through this sampling stream to intercept and gather any uranyl fluoride in the sampling stream. This filter paper is then passed by an alpha scintillation counting device where any radioactivity on the filter paper is sensed so as to provide a continuous monitoring of the gas stream for activity indicative of the uranium content in the stack gases. 1 fig.

Method for monitoring stack gases for uranium activity

DOEpatents

Beverly, Claude R.; Ernstberger, Harold G.

1988-01-01

A method for monitoring the stack gases of a purge cascade of a gaseous diffusion plant for uranium activity. A sample stream is taken from the stack gases and contacted with a volume of moisture-laden air for converting trace levels of uranium hexafluoride, if any, in the stack gases into particulate uranyl fluoride. A continuous strip of filter paper from a supply roll is passed through this sampling stream to intercept and gather any uranyl fluoride in the sampling stream. This filter paper is then passed by an alpha scintillation counting device where any radioactivity on the filter paper is sensed so as to provide a continuous monitoring of the gas stream for activity indicative of the uranium content in the stack gases.

Note: A dual temperature closed loop batch reactor for determining the partitioning of trace gases within CO2-water systems.

PubMed

Warr, Oliver; Rochelle, Christopher A; Masters, Andrew J; Ballentine, Christopher J

2016-01-01

An experimental approach is presented which can be used to determine partitioning of trace gases within CO2-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magnetic stirrer and high-pressure liquid chromatography pump, respectively.

Applications of an NMHC isotope analysis system on trace gases from plant and CARIBIC samples

NASA Astrophysics Data System (ADS)

Zuiderweg, A.; Holzinger, R.; Röckmann, T.; Brenninkmeijer, C. A. M.

2009-04-01

Isotope analysis can be a useful tool in constraining the budgets (sources and sinks) of atmospheric trace species and is increasingly applied for organic constituents. We present initial results from an automated system for isotope ratio measurements on atmospheric hydrocarbons. The inlet system is flexible and allows analysis of trace gases from medium size to large ambient air samples (5-300L) as well as CO2-concentrates from samples that have been extracted offline. Long-term testing has shown this system to be stable to 1.5‰ vs. VPDB (or better) across all tested C2-C6 compounds, and methyl chloride. This system has now been utilized to analyze emissions rates and isotopic fractionation of 7 NMHCs from Sequoia leaf litter under conditions of UV exposure. These experiments indicate, for example, δ13C depletion in methyl chloride (CH3Cl) In the range of -90 to -113 v. VPDB with continuously increasing emission rates reaching to 3.26 ng/h/gdw after constant UV exposure of 7 hours, in a dynamic reactor. Other experiments with variation in UV exposure were also undertaken, indicating variation in emission rates and δ13C with UV intensity. In addition, first results from analysis of samples from concentrates taken during the CARIBIC II (http://www.caribic-atmospheric.com/) campaign, beginning with flight 26 (return flight, Male, Maldives, to Dusseldorf, Germany, August 2000), which features flight path air originating from over the Atlantic Ocean and the Indian subcontinent, is presented.

Method and apparatus for low temperature destruction of halogenated hydrocarbons

DOEpatents

Reagen, William Kevin; Janikowski, Stuart Kevin

1999-01-01

A method and apparatus for decomposing halogenated hydrocarbons are provided. The halogenated hydrocarbon is mixed with solvating agents and maintained in a predetermined atmosphere and at a predetermined temperature. The mixture is contacted with recyclable reactive material for chemically reacting with the recyclable material to create dehalogenated hydrocarbons and halogenated inorganic compounds. A feature of the invention is that the process enables low temperature destruction of halogenated hydrocarbons.

A new class of halogen bonds that avoids the σ-hole

NASA Astrophysics Data System (ADS)

Zhang, Yu; Ma, Ning; Wang, Weizhou

2012-04-01

A new class of halogen bonds of the type X = Hal⋯Y has been investigated by using the density functional theory calculations. The strength of this new class of halogen bonds is in the range of 90-120 kcal/mol, which is greatly larger than that of the conventional halogen bond of the type X-Hal⋯Y. The geometry of this new class of halogen bonds is not determined by the halogen's positive σ-hole. Natural bond orbital analysis shows it is the n → π∗ interaction that determines the geometry of this new class of halogen bonds. Experimental results are in good agreement with the theoretical predictions.

Trans-Pacific transport and evolution of aerosols and trace gases from Asia during the INTEX-B field campaign

NASA Astrophysics Data System (ADS)

Adhikary, B.; Carmichael, G. R.; Kulkarni, S.; Wei, C.; Tang, Y.; Dallura, A.; Mena-Carrasco, M.; Streets, D. G.; Zhang, Q.; Pierce, R. B.; Al-Saadi, J. A.; Emmons, L. K.; Pfister, G. G.; Avery, M. A.; Barrick, J. D.; Blake, D. R.; Brune, W. H.; Cohen, R. C.; Dibb, J. E.; Fried, A.; Heikes, B. G.; Huey, L. G.; O'Sullivan, D. W.; Sachse, G. W.; Shetter, R. E.; Singh, H. B.; Campos, T. L.; Cantrell, C. A.; Flocke, F. M.; Dunlea, E. J.; Jimenez, J. L.; Weinheimer, A. J.; Crounse, J. D.; Wennberg, P. O.; Schauer, J. J.; Stone, E. A.; Jaffe, D. A.; Reidmiller, D. R.

2009-08-01

The Sulfur Transport and dEposition Model (STEM) developed at the University of Iowa is applied to the analysis of observations obtained during the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), conducted over the Pacific Ocean during the 2006 North American spring season. This paper reports on the model performance of meteorological parameters, trace gases, aerosols and photolysis rate (J-values) predictions with the NASA DC-8 and NSF/NCAR C-130 airborne measurements along with observations from three surface sites Mt. Bachelor, Trinidad Head and Kathmandu, Nepal. In general the model shows appreciable skill in predicting many of the important aspects of the observed distributions. The major meteorological parameters driving long range transport are accurately predicted by the WRF simulations used in this study. Furthermore, the STEM model predicts aerosols and trace gases concentrations within a standard deviation of most of the observed mean values. The results also point towards areas where model improvements are needed; e.g., the STEM model underestimates CO (15% for the DC8 and 6% for the C-130), whereas it overpredicts PAN (by a factor of two for both aircraft). The errors in the model calculations are attributed to uncertainty in emissions estimates and uncertainty in the top and lateral boundary conditions. Results from a series of sensitivity simulations examining the impact of the growth of emissions in Asia from 2000 to 2006, the importance of biomass burning, the effect of using boundary conditions from different global models, and the role of heterogeneous chemistry on the predictions are also presented. The impacts of heterogeneous reactions at specific times during dust transport episodes can be significant, and in the presence of dust both sulfate and nitrate aerosol production is increased and gas phase nitric acid levels are reduced appreciably (~50%). The aging of the air masses during the long range transport over the Pacific

Halogens and trace metal emissions from the ongoing 2008 summit eruption of Kīlauea volcano, Hawai`i

NASA Astrophysics Data System (ADS)

Mather, T. A.; Witt, M. L. I.; Pyle, D. M.; Quayle, B. M.; Aiuppa, A.; Bagnato, E.; Martin, R. S.; Sims, K. W. W.; Edmonds, M.; Sutton, A. J.; Ilyinskaya, E.

2012-04-01

Volcanic plume samples taken in 2008 and 2009 from the Halema`uma`u eruption at Kīlauea provide new insights into Kīlauea’s degassing behaviour. The Cl, F and S gas systematics are consistent with syn-eruptive East Rift Zone measurements suggesting that the new Halema`uma`u activity is fed by a convecting magma reservoir shallower than the main summit storage area. Comparison with degassing models suggests that plume halogen and S composition is controlled by very shallow (<3 m depth) decompression degassing and progressive loss of volatiles at the surface. Compared to most other global volcanoes, Kīlauea’s gases are depleted in Cl with respect to S. Similarly, our Br/S and I/S ratio measurements in Halema`uma`u’s plume are lower than those measured at arc volcanoes, consistent with contributions from the subducting slab accounting for a significant proportion of the heavier halogens in arc emissions. Analyses of Hg in Halema`uma`u’s plume were inconclusive but suggest a flux of at least 0.6 kg day-1 from this new vent, predominantly (>77%) as gaseous elemental mercury at the point of emission. Sulphate is an important aerosol component (modal particle diameter ∼0.44 μm). Aerosol halide ion concentrations are low compared to other systems, consistent with the lower proportion of gaseous hydrogen halides. Plume concentrations of many metallic elements (Rb, Cs, Be, B, Cr, Ni, Cu, Mo, Cd, W, Re, Ge, As, In, Sn, Sb, Te, Tl, Pb, Mg, Sr, Sc, Ti, V, Mn, Fe, Co, Y, Zr, Hf, Ta, Al, P, Ga, Th, U, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm) are elevated above background air. There is considerable variability in metal to SO2 ratios but our ratios (generally at the lower end of the range previously measured at Kīlauea) support assertions that Kīlauea’s emissions are metal-poor compared to other volcanic settings. Our aerosol Re and Cd measurements are complementary to degassing trends observed in Hawaiian rock suites although measured aerosol metal/S ratios

Photoacoustic trace detection of gases at the parts-per-quadrillion level with a moving optical grating.

PubMed

Xiong, Lian; Bai, Wenyu; Chen, Feifei; Zhao, Xian; Yu, Fapeng; Diebold, Gerald J

2017-07-11

The amplitude of the photoacoustic effect for an optical source moving at the sound speed in a one-dimensional geometry increases linearly in time without bound in the linear acoustic regime. Here, use of this principle is described for trace detection of gases, using two frequency-shifted beams from a CO 2 laser directed at an angle to each other to give optical fringes that move at the sound speed in a cavity with a longitudinal resonance. The photoacoustic signal is detected with a high-[Formula: see text], piezoelectric crystal with a resonance on the order of [Formula: see text] kHz. The photoacoustic cell has a design analogous to a hemispherical laser resonator and can be adjusted to have a longitudinal resonance to match that of the detector crystal. The grating frequency, the length of the resonator, and the crystal must all have matched frequencies; thus, three resonances are used to advantage to produce sensitivity that extends to the parts-per-quadrillion level.

Halogen-Mediated Conversion of Hydrocarbons to Commodities.

PubMed

Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

2017-03-08

Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

Emission Inventory of Halogenated greenhouse gases in China during 1980-2050

NASA Astrophysics Data System (ADS)

Fang, X.; Velders, G. J. M.; Ravishankara, A. R.; Molina, M.; Su, S.; Zhang, J.; Zhou, X.; Hu, J.; Prinn, R. G.

2015-12-01

China is currently the largest producer and consumer of ozone-depleting substances (ODSs) which are regulated by the Montreal Protocol (MP). Many ODSs are also powerful greenhouse gases (GHGs). The Multilateral Fund has subsidized ~1 billion US dollars for the ODS phase out in China, and thus the return on this investment is of great interest. This study gives a comprehensive emission inventory in China from 1980 to 2013 of halocarbons including ODSs and their alternatives, the hydrofluorocarbons (HFCs) that are also greenhouse gases. We then project these emissions up to 2050 according to the MP and several policy options. Total emissions of ODS and HFCs were estimated to be ~500 CO2-eq Tg/yr in 2013 which are equivalent to ~5% of total GHG emissions in China including fossil fuel CO2 emissions. Our estimate shows that China has succeeded in substantially reducing CFC-11-equivalent emissions (to protect the ozone layer), and CO2-equivalent emissions (to protect climate) of ODSs since the mid-1990s when their phase out started in China in compliance with the MP. Furthermore, the avoided CO2-eq emissions due to compliance with the MP are even greater compared to the reduced emissions, for example net cumulative avoided emissions during 19 year period between 1995-2013 are comparable to the current one year CO2 emissions from fossil fuels in China. We find that HFC CO2-eq emissions increased rapidly in last decade, which make up ~2% in 2005 to ~20% of total halocarbon CO2-eq emissions in 2013. Under a baseline scenario in which HFCs are used as alternatives in the ongoing phase out of HCFCs in China, emissions of HFCs are predicted to be important components of both China's and global future GHG emissions. However, potential exists for minimizing China's HFC emissions under mitigation scenarios. Our conclusions about China's past and future ODS and HFC emission trajectories are likely to apply to other developing countries, with important implications for mitigating

Measurements of trace contaminants in closed-type plant cultivation chambers

NASA Astrophysics Data System (ADS)

Tani, A.; Kiyota, M.; Aiga, I.; Nitta, K.; Tako, Y.; Ashida, A.; Otsubo, K.; Saito, T.

Trace contaminants generated in closed facilities can cause abnormal plant growth. We present measurement data of trace contaminants released from soils, plants, and construction materials. We mainly used two closed chambers, a Closed-type Plant and Mushroom Cultivation Chamber (PMCC) and Closed-type Plant Cultivation Equipment (CPCE). Although trace gas budgets from soils obtained in this experiment are only one example, the results indicate that the budgets of trace gases, as well as CO_2 and O_2, change greatly with the degree of soil maturation and are dependent on the kind of substances in the soil. Both in the PMCC and in the CPCE, trace gases such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), toluene and xylene were detected. These gases seemed to be released from various materials used in the construction of these chambers. The degree of increase in these trace gas levels was dependent on the relationship between chamber capacity and plant quantity. Results of trace gas measurement in the PMCC, in which lettuce and shiitake mushroom were cultivated, showed that ethylene was released both from lettuce and from the mushroom culture bed. The release rates were about 90 ng bed^-1 h^-1 for the shiitake mushroom culture bed (volume is 1700 cm^3) and 4.1 ~ 17.3 ng dm^-2h^-1 (leaf area basis) for lettuce. Higher ethylene release rates per plant and per unit leaf area were observed in mature plants than in young plants.

Using the NAME Lagrangian Particle Dispersion model, and aircraft measurements to assess the accuracy of trace gas emission inventories from the U.K.

NASA Astrophysics Data System (ADS)

O'Sullivan, D. A.; Harrison, M.; Ploson, D.; Oram, D.; Reeves, C.

2007-12-01

A top-down approach using a combination of aircraft data and atmospheric dispersion modelling has been used to estimate emissions for 24 halogenated trace gases from the United Kingdom. This has been done using data collected during AMPEP/FLUXEX, a U.K based measurement campaign which took place between April and September 2005. The primary objective relating to this work was to make direct airborne measurements of concentration enhancements within the boundary layer arising from anthropogenic pollution events, and then to use mass balance methods to determine an emission flux. This was done by analysing Whole Air Samples (WAS) collected in the boundary layer upwind and downwind of the UK at frequent intervals around the coast using the technique of gas chromatography mass spectrometry (GCMS). Emissions were then calculated using a simple box-model approach and also using NAME (Numerical Atmospheric-dispersion Modelling Environment) which is a Lagrangian particle model using 3 hourly 3D meteorology fields from the Met Office Unified Model. By using such an approach it is also possible to identify the most likely main source regions in the UK for the compounds measured. Among the trace gases studied are many which through their effects on stratospheric ozone, and their large radiative forcing have a direct impact on global climate such as CFC's 11, 12, 113 and 114, HCFC's 21, 22, 141b and 142b, HFC's 134a and 152a, methyl chloroform, methyl bromide and carbon tetrachloride. Also the emissions of some short lived gases with have direct effects on human health, such as tetrachloroethene, and trichloroethene, have been derived. The UK emissions estimates calculated from this experimental and modelling work are compared with bottom-up and other top-down emission inventories for the UK and Europe. It was found that the estimates from this study were often higher than those in bottom-up emission inventories derived from industry. In addition for a number of trace gases

Critical issues in trace gas biogeochemistry and global change.

PubMed

Beerling, David J; Nicholas Hewitt, C; Pyle, John A; Raven, John A

2007-07-15

The atmospheric composition of trace gases and aerosols is determined by the emission of compounds from the marine and terrestrial biospheres, anthropogenic sources and their chemistry and deposition processes. Biogenic emissions depend upon physiological processes and climate, and the atmospheric chemistry is governed by climate and feedbacks involving greenhouse gases themselves. Understanding and predicting the biogeochemistry of trace gases in past, present and future climates therefore demands an interdisciplinary approach integrating across physiology, atmospheric chemistry, physics and meteorology. Here, we highlight critical issues raised by recent findings in all of these key areas to provide a framework for better understanding the past and possible future evolution of the atmosphere. Incorporating recent experimental and observational findings, especially the influence of CO2 on trace gas emissions from marine algae and terrestrial plants, into earth system models remains a major research priority. As we move towards this goal, archives of the concentration and isotopes of N2O and CH4 from polar ice cores extending back over 650,000 years will provide a valuable benchmark for evaluating such models. In the Pre-Quaternary, synthesis of theoretical modelling with geochemical and palaeontological evidence is also uncovering the roles played by trace gases in episodes of abrupt climatic warming and ozone depletion. Finally, observations and palaeorecords across a range of timescales allow assessment of the Earth's climate sensitivity, a metric influencing our ability to decide what constitutes 'dangerous' climate change.

Effect of persistent trace compounds in landfill gas on engine performance during energy recovery: a case study.

PubMed

Sevimoğlu, Orhan; Tansel, Berrin

2013-01-01

Performances of gas engines operated with landfill gas (LFG) are affected by the impurities in the LFG, reducing the economic viability of energy recovery. The purpose of this study was to characterize the trace compounds in the LFG at the Odayeri Landfill, Istanbul, Turkey which is used for energy recovery. Composite gas samples were collected and analyzed for trace compounds (hydrocarbons, siloxanes, and volatile halogenated hydrocarbons) over a 3-year period. Trace compounds entering the gas engines, their impact on the engine performance were evaluated. The operational problems included deposit formation in the combustion chamber, turbocharger, and intercooler of engine before the scheduled maintenance times. High levels of hydrogen sulfide, as well as chlorinated and fluorinated compounds cause corrosion of the engine parts and decrease life of the engine oils. Persistence of siloxanes results in deposit formation, increasing engine maintenance costs. Pretreatment of LFG is necessary to protect the engines at the waste-to-energy facilities with persistence levels of siloxanes and volatile halogenated hydrocarbons. Copyright © 2012 Elsevier Ltd. All rights reserved.

Capture of trace sulfur gases from binary mixtures by single-walled carbon nanotube arrays: a molecular simulation study.

PubMed

Wang, Wenjuan; Peng, Xuan; Cao, Dapeng

2011-06-01

Adsorption of H(2)S and SO(2) pure gases and their selective capture from the H(2)S-CH(4), H(2)S-CO(2), SO(2)-N(2), and SO(2)-CO(2) binary mixtures by the single-walled carbon nanotubes (SWNT) are investigated via using the grand canonical Monte Carlo (GCMC) method. It is found that the (20, 20) SWNT with larger diameter shows larger capacity for H(2)S and SO(2) pure gases at T = 303 K, in which the uptakes reach 16.31 and 16.03 mmol/g, respectively. However, the (6,6) SWNT with small diameter exhibits the largest selectivity for binary mixtures containing trace sulfur gases at T = 303 K and P = 100 kPa. By investigating the effect of pore size on the separation of gas mixtures, we found that the optimized pore size is 0.81 nm for separation of H(2)S-CH(4), H(2)S-CO(2), and SO(2)-N(2) binary mixtures, while it is 1.09 nm for the SO(2)-CO(2) mixture. The effects of concentration and temperature on the selectivity of sulfide are also studied at the optimal pore size. It is found that the concentration (ppm) of sulfur components has little effect on selectivity of SWNTs for these binary mixtures. However, the selectivity decreases obviously with the increase of temperature. To improve the adsorption capacities, we further modify the surface of SWNTs with the functional groups. The selectivities of H(2)S-CO(2) and SO(2)-CO(2) mixtures are basically uninfluenced by the site density, while the increase of site density can improve the selectivity of H(2)S-CH(4) mixture doubly. It is expected that this work could provide useful information for sulfur gas capture.

Treatment of halogen-containing waste and other waste materials

DOEpatents

Forsberg, Charles W.; Beahm, Edward C.; Parker, George W.

1997-01-01

A process for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes.

Halogen-free boron based electrolyte solution for rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinjie; Guo, Yongsheng; Yang, Jun; Nuli, Yanna; Zhang, Fan; Wang, Jiulin; Hirano, Shin-ichi

2014-02-01

All halogen containing electrolytes for Mg battery are apt to corrode conventional metal current collectors. In this paper, a new type of halogen-free boron based electrolyte (Mg[Mes3BPh]2/THF) is designed and prepared. Electrochemical tests show that this electrolyte system possesses high ion conductivity (1.5 × 10-3 S cm-1) and good Mg deposition-dissolution reversibility. More importantly, the same electrochemical window (2.6 V vs. Mg RE) of the electrolyte on Pt and stainless steel electrodes indicates that halogen-free electrolyte indeed lessens the corrosion to conventional metal current collectors. The surface morphologies of stainless steel, aluminum and copper are further observed after their anodic potentiostatic polarization in 0.25 mol L-1 Mg[Mes3BPh]2/THF electrolyte solution for 2 days. A comparison with halogen containing electrolytes proves that the presence of halogen in electrolyte is the reason for corrosion. This work provides a stepping stone for developing new halogen-free electrolyte systems for rechargeable Mg batteries.

Investigating Planetary Volatile Accretion Mechanisms Using the Halogens

NASA Astrophysics Data System (ADS)

Ballentine, C. J.; Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Day, J. M.

2014-12-01

Depletion of the volatile elements in the Earth relative to the CI chondrites is roughly correlated with volatility, or decreasing condensation temperature. For the heavy halogen group elements (Cl, Br and I), volatility alone does not account for their apparent depletion, which early data has suggested is far greater than predicted [1-2]. Such depletion has been used to argue for the preferential loss of halogens by, amongst other processes, impact-driven erosive loss from Earth's surface [2]. Little consensus exists as to why the halogens should exhibit such preferential behavior during accretionary processes. Early efforts to constrain halogen abundance and understand their behavior in both Earth and planetary materials [3-6] have been hampered by their typically low abundance (ppb level) in most geologic materials. We present the results of halogen analysis of 23 chondrite samples, selected to represent diverse groups and petrologic type. Halogen abundances were measured by neutron irradiation noble gas mass spectrometry (NI-NGMS). Significant concentration heterogeneity is observed within some samples. However, a single Br/Cl and I/Cl ratio of 1.9 ± 0.2 (x 10-3) and 335 ± 10 (x 10-6) can be defined for carbonaceous chondrites with a good correlation between Br and Cl (R2 = 0.97) and between I and Cl (R2 = 0.84). Ratios of I/Cl overlap with terrestrial estimates of Bulk Silicate Earth and Mid Ocean Ridge Basalts. Similarly, good correlations are derived for enstatite (E) chondrites and a sulfide- and halogen- rich subset of E-chondrites. Chlorine abundances of CI (Orgueil) in this study are lower by factor of ~ 3 than the value of ~ 700 ppm Cl (compilation in [1]). Our results are similar to early discarded low values for Ivuna and Orgueil from [5,6] and agree more closely with values for CM chondrites. Halogens may not be as depleted in Earth as previously suggested, or a high degree of heterogeneity in the abundance of these volatile elements in

Application of ion-induced nucleation mass spectrometry in the analysis of trace gases evolved from a polyimide film during the thermal curing stages

NASA Technical Reports Server (NTRS)

Smith, A. C.

1982-01-01

Trace gases evolved from a polyimide film during its thermal curing stages have been studied using ion-induced nucleation mass spectrometry. The technique involved exposing the test gas sample to a low energy beta source and recording the masses of the ion-induced molecular clusters formed in the reaction chamber. On the basis of the experimentally observed molecular cluster spectra, it has been concluded that the dominant trace component had a molecular weight of 87 atomic mass units. This component has been identified as a molecule of dimethylacetamide (DMAC) which had been used as a solvent in the preparation of the test polyimide specimen. This identification has been further confirmed by comparing the spectra of the test gas sample and the DMAC calibration sample obtained with a conventional mass spectrometer. The advantages of the ion-induced nucleation mass spectrometer versus the conventional mass spectrometer are discussed.

Treatment of halogen-containing waste and other waste materials

DOEpatents

Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

1997-03-18

A process is described for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes. 3 figs.

Method for halogenating or radiohalogenating a chemical compound

DOEpatents

Kabalka, George W.

2006-05-09

A method for obtaining a halogenated organic compound, whereby an organotrifluoroborate compound is reacted with a halide ion in the presence of an oxidizing agent to produce the corresponding halogenated organic compound. The method may be used for producing radiohalogenated organic compounds.

The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances

PubMed Central

2013-01-01

Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to

Pilot-scale incineration of wastes with high content of chlorinated and non-halogenated organophosphorus flame retardants used as alternatives for PBDEs.

PubMed

Matsukami, Hidenori; Kose, Tomohiro; Watanabe, Mafumi; Takigami, Hidetaka

2014-09-15

Chlorinated and non-halogenated organophosphorus flame retardants (OPFRs) including tris(2-chloroisopropyl) phosphate (TCIPP), diethylene glycol bis(di(2-chloroisopropyl) phosphate) (DEG-BDCIPP), triphenyl phosphate (TPHP), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) have been used increasingly as alternatives to polybrominated diphenyl ethers and other brominated flame retardants. For this study, five batches of incineration experiments of wastes containing approximately 1% of TCIPP, DEG-BDCIPP, TPHP, and BPA-BDPP were conducted using a pilot-scale incinerator. Destruction and emission behaviors of OPFRs were investigated along with the effects on behaviors of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and pentachlorophenol (PCP). Incineration conditions were chosen according to current regulations for waste incinerators in Japan and UNEP. The OPFRs in the input materials were mainly destroyed in the primary combustion with destruction efficiencies greater than 99.999%. Concentrations of the OPFRs in the exhaust gases and ash were, respectively, <0.01-0.048 μg m(-3) and <0.5-68 μg kg(-1). Almost all of the total phosphorus in the input materials was partitioned into the ash, but less into final exit gases, indicating negligible emissions of volatile phosphorus compounds during incineration. Inputs of chlorinated OPFRs did not affect the formation markedly. Destruction and emission behaviors of unintentional POPs were investigated. Emissions of such POPs in exhaust gases and the ash were lower than the Japanese and international standards. Results show that even in wastes with high contents of chlorinated and non-halogenated OPFRs, waste incineration by the current regulations for the waste incinerators can control environmental emissions of OPFRs and

Scientific conferences: A big hello to halogen bonding

NASA Astrophysics Data System (ADS)

Erdelyi, Mate

2014-09-01

Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

Trace gas emissions from the marine biosphere.

PubMed

Liss, Peter S

2007-07-15

A wide variety of trace gases (e.g. dimethyl sulphide, organohalogens, ammonia, non-methane and oxygenated hydrocarbons, volatile oxygenated organics and nitrous oxide) are formed in marine waters by biological and photochemical processes. This leads in many, but not all, cases to supersaturation of the water relative to marine air concentrations and a net flux of trace gas to the atmosphere. Since the gases are often in their reduced forms in the water, once in the atmosphere they are subject to oxidation by photolysis or radical attack to form chemically reactive species that can affect the oxidizing capacity of the air. They can also lead to the formation of new particles or the growth of existing ones that can then contribute to both direct and indirect (via the formation of cloud condensation nuclei) aerosol effects on climate. These cycles are discussed with respect to their impacts on the chemistry of the atmosphere, climate and human health. This whole topic was the subject of an extensive review (Nightingale & Liss 2003 In Treatise in geochemistry (eds H. D. Holland & K. K. Turekian), pp. 49-81) and what will be attempted here is a brief update of the earlier paper. There is no attempt to be comprehensive either in terms of gases covered or to give a complete review of all the recent literature. It is a personal view of recent advances both from my own research group as well as significant work from others. Questions raised at the meeting 'Trace gas biogeochemistry and global change' are dealt with at appropriate places in the text (rather than at the end of the piece). Discussion of each of the gases or group of gases is given in the following separate sections.

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

Infrared measurements of atmospheric gases above Mauna Loa, Hawaii, in February 1987

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Murcray, F. H.; Blatherwick, R. D.

1988-01-01

The IR absorptions spectra of 13 minor and trace atmospheric gases, recorded by the NOAA's Geophysical Monitoring for Climate Change (GMCC) program station at Mauna Loa, Hawaii, for four days in February 1987, were analyzed to determine simultaneous total vertical column amounts for these gases. Comparisons with other data indicate that the NOAA GMCC surface volume mixing ratios are good measures of the mean volume mixing ratios of these gases in the troposphere and that Mauna Loa is a favorable site for IR monitoring of atmospheric gases. The ozone total columns deduced from the IR spectra agreed with the correlative Umkehr observations.

The Important Role of Halogen Bond in Substrate Selectivity of Enzymatic Catalysis

NASA Astrophysics Data System (ADS)

Jiang, Shuiqin; Zhang, Lujia; Cui, Dongbin; Yao, Zhiqiang; Gao, Bei; Lin, Jinping; Wei, Dongzhi

2016-10-01

The use of halogen bond is widespread in drug discovery, design, and clinical trials, but is overlooked in drug biosynthesis. Here, the role of halogen bond in the nitrilase-catalyzed synthesis of ortho-, meta-, and para-chlorophenylacetic acid was investigated. Different distributions of halogen bond induced changes of substrate binding conformation and affected substrate selectivity. By engineering the halogen interaction, the substrate selectivity of the enzyme changed, with the implication that halogen bond plays an important role in biosynthesis and should be used as an efficient and reliable tool in enzymatic drug synthesis.

Tropospheric impacts of volcanic halogen emissions: first simulations of reactive halogen chemistry in the Eyjafjallajökull eruption plume

NASA Astrophysics Data System (ADS)

Roberts, Tjarda

2013-04-01

Volcanic plumes are regions of high chemical reactivity. Instrumented research aircraft that probed the 2010 Icelandic Eyjafjallajökull eruption plume identified in-plume ozone depletion and reactive halogens (Cl, BrO), the latter also detected by satellite. These measurements add to growing evidence that volcanic plumes support rapid reactive halogen chemistry, with predicted impacts including depletion of atmospheric oxidants and mercury deposition. However, attempts to simulate volcanic plume halogen chemistry and predict impacts are subject to considerable uncertainties. e.g. in rate constants for HOBr reactive uptake (see this session: EGU2013-6076), or in the high-temperature initialisation. Model studies attempting to replicate volcanic plume halogen chemistry are restricted by a paucity of field data that is required both for model tuning and verification, hence reported model 'solutions' are not necessarily unique. To this end, the aircraft, ground-based and satellite studies of the Eyjafjallajökull eruption provide a valuable combination of datasets for improving our understanding of plume chemistry and impacts. Here, PlumeChem simulations of Eyjafjallajökull plume reactive halogen chemistry and impacts are presented and verified by observations for the first time. Observed ozone loss, a function of plume strength and age, is quantitatively reproduced by the model. Magnitudinal agreement to reported downwind BrO and Cl is also shown. The model predicts multi-day impacts, with reactive bromine mainly as BrO, HOBr and BrONO2 during daytime, and Br2 and BrCl at night. BrO/SO2 is reduced in more dispersed plumes due to enhanced partitioning to HOBr, of potential interest to satellite studies of BrO downwind of volcanoes. Additional predicted impacts of Eyjafjallajökull volcanic plume halogen chemistry include BrO-mediated depletion of HOx that reduces the rate of SO2 oxidation to H2SO4, hence the formation of sulphate aerosol. The model predicts NOx is

Halogen bonding based recognition processes: a world parallel to hydrogen bonding.

PubMed

Metrangolo, Pierangelo; Neukirch, Hannes; Pilati, Tullio; Resnati, Giuseppe

2005-05-01

Halogen bonding is the noncovalent interaction between halogen atoms (Lewis acids) and neutral or anionic Lewis bases. The main features of the interaction are given, and the close similarity with the hydrogen bonding will become apparent. Some heuristic principles are presented to develop a rational crystal engineering based on halogen bonding. The focus is on halogen-bonded supramolecular architectures given by halocarbons. The potential of the interaction is shown by useful applications in the field of synthetic chemistry, material science, and bioorganic chemistry.

Trace Gas Retrievals from the GeoTASO Aircraft Instrument During the DISCOVER-AQ Campaigns

NASA Astrophysics Data System (ADS)

Nowlan, C. R.; Liu, X.; Leitch, J. W.; Liu, C.; Gonzalez Abad, G.; Chance, K.; Delker, T.; Good, W. S.; Murcray, F.; Ruppert, L.; Kaptchen, P. F.; Loughner, C.; Follette-Cook, M. B.; Pickering, K. E.

2014-12-01

The Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) instrument is a recently-developed passive remote sensing instrument capable of making 2-D measurements of trace gases from aircraft. GeoTASO was developed under NASA's Instrument Incubator program and is a test-bed instrument for the Geostationary Coastal and Air Pollution Events (GEO-CAPE) decadal survey and the upcoming Tropospheric Emissions: Monitoring of Pollution (TEMPO) satellite missions. The instrument collects spectra of backscattered UV-visible radiation for the detection of tropospheric trace gases such as NO2, ozone, formaldehyde and SO2. GeoTASO flew on the NASA HU-25C Falcon aircraft during the 2013 (Texas) and 2014 (Colorado) DISCOVER-AQ field campaigns, making satellite-analog measurements of trace gases at a spatial resolution of approximately 500x500 m over urban areas, power plants and other industrial sources of pollution. We present the GeoTASO retrieval algorithms, trace gas measurement results, and validation comparisons with ground-based observations and other aircraft instruments during these campaigns.

Note: A dual temperature closed loop batch reactor for determining the partitioning of trace gases within CO{sub 2}-water systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warr, Oliver, E-mail: oliver.warr@earth.ox.ac.uk; Ballentine, Christopher J.; Rochelle, Christopher A.

An experimental approach is presented which can be used to determine partitioning of trace gases within CO{sub 2}-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magneticmore » stirrer and high-pressure liquid chromatography pump, respectively.« less

Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

PubMed Central

Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B

1985-01-01

A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371

Field measurements of trace gases and aerosols emitted by peat fires in Central Kalimantan, Indonesia, during the 2015 El Niño

NASA Astrophysics Data System (ADS)

Stockwell, Chelsea E.; Jayarathne, Thilina; Cochrane, Mark A.; Ryan, Kevin C.; Putra, Erianto I.; Saharjo, Bambang H.; Nurhayati, Ati D.; Albar, Israr; Blake, Donald R.; Simpson, Isobel J.; Stone, Elizabeth A.; Yokelson, Robert J.

2016-09-01

Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional-global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs; grams of a compound per kilogram biomass burned) for up to ˜ 90 gases, including CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n = 35), indicating essentially pure smoldering combustion, and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g kg-1) were carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision

Electroreduction of Halogenated Organic Compounds

NASA Astrophysics Data System (ADS)

Rondinini, Sandra; Vertova, Alberto

The electroreductive cleavage of the carbon-halogen bond in halogenated organic compounds has been extensively studied for more than 70 years, since it is prodromal to a large variety of synthetic applications in organic electrochemistry. Over the years the research interest have progressively included the environmental applications, since several organic halocompounds are known to have (or have had) a serious environmental impact because of their (present or past) wide use as cleaning agents, herbicides, cryogenic fluids, reagents (e.g. allyl and vinyl monomers) for large production materials, etc. Recent studies have also demonstrated the wide spread out- and in-door-presence of volatile organic halides, although at low level, in connexion with residential and non-residential (e.g. stores, restaurants and transportation) activities. In this context, the detoxification of emissions to air, water and land by the selective removal of the halogen group represents a valid treatment route, which, although not leading to the complete mineralization of the pollutants, produces less harmful streams to be easily treated by electrochemical or conventional techniques. The electroreduction process is analysed and discussed in terms of electrode material, reaction medium, cell design and operation, and of substrate classification.

[Remote sensing of atmospheric trace gas by airborne passive FTIR].

PubMed

Gao, Min-quang; Liu, Wen-qing; Zhang, Tian-shu; Liu, Jian-guo; Lu, Yi-huai; Wang, Ya-ping; Xu, Liang; Zhu, Jun; Chen, Jun

2006-12-01

The present article describes the details of aviatic measurement for remote sensing trace gases in atmosphere under various surface backgrounds with airborne passive FTIR. The passive down viewing and remote sensing technique used in the experiment is discussed. The method of acquiring atmospheric trace gases infrared characteristic spectra in complicated background and the algorithm of concentration retrieval are discussed. The concentrations of CO and N2O of boundary-layer atmosphere in experimental region below 1000 m are analyzed quantitatively. This measurement technique and the data analysis method, which does not require a previously measured background spectrum, allow fast and mobile remote detection and identification of atmosphere trace gas in large area, and also can be used for urgent monitoring of pollution accidental breakout.

Structures and electronic states of halogen-terminated graphene nano-flakes

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Iyama, Tetsuji

2015-12-01

Halogen-functionalized graphenes are utilized as electronic devices and energy materials. In the present paper, the effects of halogen-termination of graphene edge on the structures and electronic states of graphene flakes have been investigated by means of density functional theory (DFT) method. It was found that the ionization potential (Ip) and electron affinity of graphene (EA) are blue-shifted by the halogen termination, while the excitation energy is red-shifted. The drastic change showed a possibility as electronic devices such as field-effect transistors. The change of electronic states caused by the halogen termination of graphene edge was discussed on the basis of the theoretical results.

40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

Halogen speciation in volcanic plumes - Development of compact denuder sampling techniques with in-situ derivatization followed by gas chromatography-mass spectrometry and their application at Mt. Etna, Mt. Nyiragongo and Mt. Nyamulagira in 2015.

NASA Astrophysics Data System (ADS)

Rüdiger, Julian; Bobrowski, Nicole; Hoffmann, Thorsten

2016-04-01

Volcanoes are a large source for several reactive atmospheric trace gases including sulfur and halogen containing species. The detailed knowledge of volcanic plume chemistry can give insights into subsurface processes and can be considered as a useful geochemical tool for monitoring of volcanic activity, especially halogen to sulfur ratios (e.g. Bobrowski and Giuffrida, 2012; Donovan et al., 2014). The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable by UV spectrometer at a safe distance. Furthermore it is formed in the plume by a multiphase reaction mechanism under depletion of ozone in the plume. The abundance of BrO changes as a function of the reaction time and therefore distance from the vent as well as the spatial position in the plume. The precursor substance for the formation of BrO is HBr with Br2as an intermediate product. The reaction of HBr to BrO involves heterogeneous reactions involving aerosol particles, while Br2 reacts directly with O3 to form BrO in a UV radiation induced mechanism. Due to the lack of analytical approaches for the species analysis of halogens (HBr, Br2, Br, BrCl, HOBr) there are still uncertainties about the magnitude of volcanic halogen emissions and in particular their speciation and therefore also in the understanding of the bromine chemistry in volcanic plumes (Bobrowski et al., 2007). In this study a gas diffusion denuder sampling method using a 1,3,5-trimethoxybenzene (1,3,5-TMB) coating for the derivatization of reactive halogen species (Rüdiger et al., 2015) was characterized by reaction chamber experiments. The coating proved to be suitable to collect selectively gaseous bromine species with oxidation states of +1 or 0 (such as Br2, BrCl, BrO(H) and BrONO2), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with reactive bromine species gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding

Variations of trace gases over the Bay of Bengal during the summer monsoon

NASA Astrophysics Data System (ADS)

Girach, I. A.; Ojha, Narendra; Nair, Prabha R.; Tiwari, Yogesh K.; Kumar, K. Ravi

2018-02-01

In situ measurements of near-surface ozone (O3), carbon monoxide (CO), and methane (CH4) were carried out over the Bay of Bengal (BoB) as a part of the Continental Tropical Convergence Zone (CTCZ) campaign during the summer monsoon season of 2009. O3, CO and CH4 mixing ratios varied in the ranges of 8-54 ppbv, 50-200 ppbv and 1.57-2.15 ppmv, respectively during 16 July-17 August 2009. The spatial distribution of mean tropospheric O3 from satellite retrievals is found to be similar to that in surface O3 observations, with higher levels over coastal and northern BoB as compared to central BoB. The comparison of in situ measurements with the Monitoring Atmospheric Composition & Climate (MACC) global reanalysis shows that MACC simulations reproduce the observations with small mean biases of 1.6 ppbv, -2.6 ppbv and 0.07 ppmv for O3, CO and CH4, respectively. The analysis of diurnal variation of O3 based on observations and the simulations from Weather Research and Forecasting coupled with Chemistry (WRF-Chem) at a stationary point over the BoB did not show a net photochemical build up during daytime. Satellite retrievals show limitations in capturing CH4 variations as measured by in situ sample analysis highlighting the need of more shipborne in situ measurements of trace gases over this region during monsoon.

Metal halogen battery system with multiple outlet nozzle for hydrate

DOEpatents

Bjorkman, Jr., Harry K.

1983-06-21

A metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, store means whereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former whereby the hydrate is formed in association with the store means, said store means being constructed in the form of a container which includes a filter means, said filter means being inoperative to separate the hydrate formed from the electrolyte, said system having, a hydrate former pump means associated with the store means and being operative to intermix halogen gas with aqueous electrolyte to form halogen hydrate, said hydrate former means including, multiple outlet nozzle means connected with the outlet side of said pump means and being operative to minimize plugging, said nozzle means being comprised of at least one divider means which is generally perpendicular to the rotational axes of gears within the pump means, said divider means acting to divide the flow from the pump means into multiple outlet flow paths.

Trace gas emissions from chaparral and boreal forest fires

NASA Technical Reports Server (NTRS)

Cofer, Wesley R., III; Levine, Joel S.; Sebacher, Daniel I.; Winstead, Edward L.; Riggan, Philip J.; Stocks, Brian J.; Brass, James A.; Ambrosia, Vincent G.

1989-01-01

Using smoke samples collected during low-level helicopter flights, the mixing ratios of CO2, CO, CH4, total nonmethane hydrocarbons, H2, and N2O over burning chaparral in southern California and over a burning boreal forest site in northern Ontario, Canada, were determined. Carbon dioxide-normalized emission ratios were determined for each trace gas for conditions of flaming, mixed, and smoldering combustion. The emission ratios for these trace gases were found to be highest for the smoldering combustion, generally thought to be the least efficient combustion stage. However, high emission ratios for these gases could be also produced during very vigorous flaming combustion.

Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

NASA Technical Reports Server (NTRS)

Smith, G. B.

1996-01-01

The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

The unique role of halogen substituents in the design of modern agrochemicals.

PubMed

Jeschke, Peter

2010-01-01

The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

Trace element geochemistry of volcanic gases and particles from 1983-1984 eruptive episodes of Kilauea Volcano

NASA Astrophysics Data System (ADS)

Crowe, Bruce M.; Finnegan, David L.; Zoller, William H.; Boynton, William V.

1987-12-01

Compositional data have been obtained for volcanic gases and particles collected from fume emitted at the Pu'u O'o vent on the east rift zone of Kilauea volcano. The samples were collected by pumping fume through a filter pack system consisting of a front stage particulate filter followed by four base-treated filters (7LiOH). Particles and condensed phases are trapped on the particulate filter, and acidic gases are collected on the treated filters. The filters are analyzed for 30 elements by instrumental neutron activation analysis. Fume samples were collected from the Pu'u O'o vent for two eruptive episodes: (1) 7 days after episode 11 (cooling vent samples) and (2) the waning stage of episode 13 (active vent samples). Additional samples were collected by aircraft from the gas plume released during the lava fountaining phase of episode 17 (aircraft samples). Element concentrations in the vent gases were > 104 μg m-3 for S, Cl, and F. Enrichment factors (EFs) for the volcanic fume versus the source magma were calculated using the volatile element Br as the reference element for normalization and the U.S. Geological Survey standard BHVO-1 as the magma standard. This removes the ash dilution effect obtained by using an ash constituent (Al, Sc, or Mg) as the reference element. Bromine-normalized EFs (× 105) range from 101 to 102 for Na, K, and Cu; 102 to 105 for Zn, W, Sb, In, Ir, Ag, F, and As; and > 105 for Au, Cd, Re, Cl, Se, and S. The highest enrichment factors are for aircraft samples collected during the most gas-rich phase of an eruption cycle. Metal and volatile-element data form two groups: (1) elements showing little or no variation in abundance ratios with sample type (group 1: Cl, Br, and Re) and (2) elements that show significant variation in abundance ratios by sample type (group 2: Zn, W, Sb, In, Ir, Au, and Cd). Bivariate plots of elements of the first group versus elements of the second group separate by sample type. The separation corresponds to

Response of trace gases to the disrupted 2015-2016 quasi-biennial oscillation

NASA Astrophysics Data System (ADS)

Tweedy, Olga V.; Kramarova, Natalya A.; Strahan, Susan E.; Newman, Paul A.; Coy, Lawrence; Randel, William J.; Park, Mijeong; Waugh, Darryn W.; Frith, Stacey M.

2017-06-01

The quasi-biennial oscillation (QBO) is a quasiperiodic alternation between easterly and westerly zonal winds in the tropical stratosphere, propagating downward from the middle stratosphere to the tropopause with a period that varies from 24 to 32 months ( ˜ 28 months on average). The QBO wind oscillations affect the distribution of chemical constituents, such as ozone (O3), water vapor (H2O), nitrous oxide (N2O), and hydrochloric acid (HCl), through the QBO-induced meridional circulation. In the 2015-2016 winter, radiosonde observations revealed an anomaly in the downward propagation of the westerly phase, which was disrupted by the upward displacement of the westerly phase from ˜ 30 hPa up to 15 hPa and the sudden appearance of easterlies at 40 hPa. Such a disruption is unprecedented in the observational record from 1953 to the present. In this study we show the response of trace gases to this QBO disruption using O3, HCl, H2O, and temperature from the Aura Microwave Limb Sounder (MLS) and total ozone measurements from the Solar Backscatter Ultraviolet (SBUV) Merged Ozone Data Set (MOD). Results reveal the development of positive anomalies in stratospheric equatorial O3 and HCl over ˜ 50-30 hPa in May-September of 2016 and a substantial decrease in O3 in the subtropics of both hemispheres. The SBUV observations show near-record low levels of column ozone in the subtropics in 2016, resulting in an increase in the surface UV index during northern summer. Furthermore, cold temperature anomalies near the tropical tropopause result in a global decrease in stratospheric water vapor.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

Retrieval of trace gas concentrations over Summit Station, Greenland using moderate-resolution spectral infrared radiances

NASA Astrophysics Data System (ADS)

Bahramvash Shams, S.; Walden, V. P.; Turner, D. D.

2017-12-01

Measurements of trace gases at high temporal resolution are important for understanding variations and trends at high latitudes. Trace gases over Greenland can be influenced by both long-range transport from pollution sources as well as local chemical processes. Satellite retrievals are an important data source in the polar regions, but accurate ground-based measurements are needed for proper validation, especially in data sparse regions. A moderate-resolution (0.5 cm-1) Fourier transform infrared spectrometer (FTIR), the Polar Atmospheric Emitted Radiance Interferometer (P-AERI), has been operated at Summit Station, Greenland as part of the ICECAPS project since 2010. In this study, trace gas concentrations, including ozone, nitrous oxide, and methane are retrieved using different optimal estimation retrieval codes. We first present results of retrieved gases using synthetic spectra (from a radiative transfer model) that mimic P-AERI measurements to evaluate systematic errors in the inverse models. We also retrieve time series of trace gas concentrations during periods of clear skies over Summit. We investigate the amount of vertical information that can be obtained with moderate resolution spectra for each of the trace gases, and also the impact of the seasonal variation of atmospheric water vapor on the retrievals. Data from surface observations and ozonesondes obtained by the NOAA Global Monitoring Division are used to improve the retrievals and as validation.

Trace gases over Northern Eurasia: background level and disturbing factors

NASA Astrophysics Data System (ADS)

Skorokhod, A.; Shumsky, R.; Pankratova, N.; Moiseenko, K.; Vasileva, A.; Berezina, E.; Elansky, N.

2012-04-01

Atmospheric air composition over the vast and low inhabited areas of Northern Eurasia is still poorly studied because of lack of the precise direct measurements. This harms to accuracy of both global and regional models which simulate climatological and ecosystem changes in that highly important region. In this work background trace gases (such as O3, NO, NO2, CO) concentrations and their variability are considered on base of results of continuous measurements at ZOTTO station in the middle of Siberia which have been carried out since March, 2007. Also factors implying background regime (like long-range transport, wild fires emissions) are analyzed. To compliment study data of TROICA train-based campaigns which have been regularly provided across Russia for many years (1995-2010) are used. The concentration of ozone has a pronounced seasonal variation with a clear peak in spring (40-45 ppbv in average and up to 80 ppbv in extreme cases) and minimum in winter. Average ozone level is about 20 ppbv that corresponds to the background conditions. Enhanced concentration in March-July is due to increased stratospheric-tropospheric exchange. In autumn and winter distribution of ozone is close to uniform. Photochemical processes under low light and air temperature does not cause the generation of ozone. Sink on the snow surface is very small, and therefore the diurnal variations are absent. In general, seasonal variations correspond to the average seasonal course, which is typical for Russia. The analysis of diurnal ozone variations in Zotino in different seasons showed that the maximum rate of ozone formation is observed in summer from 9 to 15 h local time and is 1-2 ppbv/hour. It correlates well with the data on the isoprene emissions and others biogenic VOC reacting with OH- radical. Thus they are biogenic VOC emissions that seem to be the main factor of the lower troposphere oxidation power in summer. In other seasons it is significantly lower. NOx concentration does

Dissolved organic matter composition drives the marine production of brominated very short-lived substances.

PubMed

Liu, Yina; Thornton, Daniel C O; Bianchi, Thomas S; Arnold, William A; Shields, Michael R; Chen, Jie; Yvon-Lewis, Shari A

2015-03-17

Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

Halogen Bonding: A Powerful Tool for Modulation of Peptide Conformation

PubMed Central

2017-01-01

Halogen bonding is a weak chemical force that has so far mostly found applications in crystal engineering. Despite its potential for use in drug discovery, as a new molecular tool in the direction of molecular recognition events, it has rarely been assessed in biopolymers. Motivated by this fact, we have developed a peptide model system that permits the quantitative evaluation of weak forces in a biologically relevant proteinlike environment and have applied it for the assessment of a halogen bond formed between two amino acid side chains. The influence of a single weak force is measured by detection of the extent to which it modulates the conformation of a cooperatively folding system. We have optimized the amino acid sequence of the model peptide on analogues with a hydrogen bond-forming site as a model for the intramolecular halogen bond to be studied, demonstrating the ability of the technique to provide information about any type of weak secondary interaction. A combined solution nuclear magnetic resonance spectroscopic and computational investigation demonstrates that an interstrand halogen bond is capable of conformational stabilization of a β-hairpin foldamer comparable to an analogous hydrogen bond. This is the first report of incorporation of a conformation-stabilizing halogen bond into a peptide/protein system, and the first quantification of a chlorine-centered halogen bond in a biologically relevant system in solution. PMID:28581720

Extending Halogen-based Medicinal Chemistry to Proteins

PubMed Central

El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B.; Smith, Brian J.; Menting, John G.; Whittaker, Jonathan; Lawrence, Michael C.; Meuwly, Markus; Weiss, Michael A.

2016-01-01

Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (TyrB26) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-TyrB26]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (TyrB16, PheB24, PheB25, 3-I-TyrB26, and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-TyrB26]insulin analog (determined as an R6 zinc hexamer). Given that residues B24–B30 detach from the core on receptor binding, the environment of 3-I-TyrB26 in a receptor complex must differ from that in the free hormone. Based on the recent structure of a “micro-receptor” complex, we predict that 3-I-TyrB26 engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such “halogen engineering” promises to extend principles of medicinal chemistry to proteins. PMID:27875310

Implementation of marine halogen chemistry into the Community Multiscale Air Quality (CMAQ) model

NASA Astrophysics Data System (ADS)

Gantt, B.; Sarwar, G.

2017-12-01

In two recent studies (Sarwar et al, 2015 and Gantt et al., 2017), the impact of marine halogen (bromine and iodine) chemistry on air quality has been evaluated using the Community Multiscale Air Quality (CMAQ) model. We found that marine halogen chemistry not only has the expected effect of reducing marine boundary layer ozone concentrations, but also reduces ozone in the free troposphere and inland from the coast. In Sarwar et al. (2015), the impact of the halogen chemistry without and with photochemical reactions of higher iodine oxides over the Northern Hemisphere was examined using the coarse horizontal grids of a hemispheric domain. Halogen chemistry without and with the photochemical reactions of higher iodine oxides reduces ozone over seawater by 15% and 48%, respectively. Using the results of the chemistry without the photochemical reactions of higher iodine oxides, we developed a simple first order ozone loss rate and implemented it into the public version of CMAQv52. In Gantt et al. (2017), the impact of the simple first order loss rate as well as the full halogen chemistry without photochemical reactions of higher iodine oxides over the continental United States was examined using finer horizontal grids of the regional domain and boundary conditions from the hemispheric domain with and without marine halogen chemistry. The boundary conditions obtained with the halogen chemistry as well as the simple halogen chemistry reduces ozone along the coast where CMAQ typically overpredicts the concentrations. Development of halogen chemistry in CMAQ has continued with the implementation of several heterogeneous reactions of bromine and iodine species, revised reactions of higher iodine oxides, and a refined marine halogen emissions inventory. Our latest version of halogen chemistry with photochemical reactions of higher iodine oxides reduces ozone by 23% over the seawater. This presentation will discuss the previous and ongoing implementation of revised halogen

40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is subject...

40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is subject...

Biomass burning emissions of trace gases and particles in marine air at Cape Grim, Tasmania

NASA Astrophysics Data System (ADS)

Lawson, S. J.; Keywood, M. D.; Galbally, I. E.; Gras, J. L.; Cainey, J. M.; Cope, M. E.; Krummel, P. B.; Fraser, P. J.; Steele, L. P.; Bentley, S. T.; Meyer, C. P.; Ristovski, Z.; Goldstein, A. H.

2015-12-01

(ΔO3 / ΔCO 0.001-0.074). A short-lived increase in NMOCs by a factor of 10 corresponded with a large CO enhancement, an increase of the NMOC / CO emission ratio (ER) by a factor of 2-4 and a halving of the BC / CO ratio. Rainfall on Robbins Island was observed by radar during this period which likely resulted in a lower fire combustion efficiency, and higher emission of compounds associated with smouldering. This highlights the importance of relatively minor meteorological events on BB emission ratios. Emission factors (EFs) were derived for a range of trace gases, some never before reported for Australian fires, (including hydrogen, phenol and toluene) using the carbon mass balance method. This provides a unique set of EFs for Australian coastal heathland fires. Methyl halide EFs were higher than EFs reported from other studies in Australia and the Northern Hemisphere which is likely due to high halogen content in vegetation on Robbins Island. This work demonstrates the substantial impact that BB plumes can have on the composition of marine air, and the significant changes that can occur as the plume interacts with terrestrial, aged urban and marine emission sources.

Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

PubMed

Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

2018-05-01

The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes.

PubMed

Fanfrlík, Jindřich; Holub, Josef; Růžičková, Zdeňka; Řezáč, Jan; Lane, Paul D; Wann, Derek A; Hnyk, Drahomír; Růžička, Aleš; Hobza, Pavel

2016-11-04

Halogen bonds are a subset of noncovalent interactions with rapidly expanding applications in materials and medicinal chemistry. While halogen bonding is well known in organic compounds, it is new in the field of boron cluster chemistry. We have synthesized and crystallized carboranes containing Br atoms in two different positions, namely, bound to C- and B-vertices. The Br atoms bound to the C-vertices have been found to form halogen bonds in the crystal structures. In contrast, Br atoms bound to B-vertices formed hydrogen bonds. Quantum chemical calculations have revealed that halogen bonding in carboranes can be much stronger than in organic architectures. These findings open new possibilities for applications of carboranes, both in materials and medicinal chemistry. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing California groundwater susceptibility using trace concentrations of halogenated volatile organic compounds

USGS Publications Warehouse

Deeds, Daniel A.; Kulongoski, Justin T.; Belitz, Kenneth

2012-01-01

Twenty-four halogenated volatile organic compounds (hVOCs) and SF6 were measured in groundwater samples collected from 312 wells across California at concentrations as low as 10–12 grams per kilogram groundwater. The hVOCs detected are predominately anthropogenic (i.e., “ahVOCs”) and as such their distribution delineates where groundwaters are impacted and susceptible to human activity. ahVOC detections were broadly consistent with air-saturated water concentrations in equilibrium with a combination of industrial-era global and regional hVOC atmospheric abundances. However, detection of ahVOCs in nearly all of the samples collected, including ancient groundwaters, suggests the presence of a sampling or analytical artifact that confounds interpretation of the very-low concentration ahVOC data. To increase our confidence in ahVOC detections we establish screening levels based on ahVOC concentrations in deep wells drawing ancient groundwater in Owens Valley. Concentrations of ahVOCs below the Owens Valley screening levels account for a large number of the detections in prenuclear groundwater across California without significant loss of ahVOC detections in shallow, recently recharged groundwaters. Over 80% of the groundwaters in this study contain at least one ahVOC after screening, indicating that the footprint of human industry is nearly ubiquitous and that most California groundwaters are vulnerable to contamination from land-surface activities.

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: A Review

PubMed Central

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-01-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical, and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter, or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article. PMID:29755967

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

NASA Astrophysics Data System (ADS)

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-04-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

The effect of varying halogen substituent patterns on the cytochrome P450 catalysed dehalogenation of 4-halogenated anilines to 4-aminophenol metabolites.

PubMed

Cnubben, N H; Vervoort, J; Boersma, M G; Rietjens, I M

1995-05-11

The cytochrome P450 catalysed biotransformation of 4-halogenated anilines was studied in vitro with special emphasis on the dehalogenation to 4-aminophenol metabolites. The results demonstrated that a fluorine substituent at the C4 position was more easily eliminated from the aromatic ring than a chloro-, bromo- or iodo-substituent. HPLC analysis of in vitro biotransformation patterns revealed that the dehalogenation of the C4-position was accompanied by formation of non-halogenated 4-aminophenol, without formation of NIH-shifted metabolites. Changes in the apparent Vmax for the microsomal oxidative dehalogenation appeared to correlate with the electronegativity of the halogen substituent at C4, the fluorine substituent being the one most easily eliminated. A similar decrease in the rate of dehalogenation from a fluoro- to a chloro- to a bromo- to an iodo-substituent was observed in a system with purified reconstituted cytochrome P450 IIB1, in a tertiair butyl hydroperoxide supported microsomal cytochrome P450 system as well as in a system with microperoxidase 8. This microperoxidase 8 is a haem-based mini-enzyme without a substrate binding site, capable of catalysing cytochrome P450-like reaction chemistry. Together, these results excluded the possibility that the difference in the rate of dehalogenation with a varying C4-halogen substituent arose from a change in the contribution of cytochrome P450 enzymes involved in oxidative dehalogenation with a change in the halogen substituent. Rather, they strongly suggested that the difference was indeed due to an intrinsic electronic parameter of the various C4 halogenated anilines dependent on the type of halogen substituent. Additional in vitro experiments with polyfluorinated anilines demonstrated that elimination of the C4-fluorine substituent became more difficult upon the introduction of additional electron withdrawing fluorine substituents in the aniline-ring. 19F-NMR analysis of the metabolite patterns showed

A new WRF-Chem treatment for studying regional-scale impacts of cloud processes on aerosol and trace gases in parameterized cumuli

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L. K.; Shrivastava, M.; Easter, R. C.

A new treatment of cloud effects on aerosol and trace gases within parameterized shallow and deep convection, and aerosol effects on cloud droplet number, has been implemented in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) version 3.2.1 that can be used to better understand the aerosol life cycle over regional to synoptic scales. The modifications to the model include treatment of the cloud droplet number 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 convectivemore » cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. These changes have been implemented in both the WRF-Chem chemistry packages as well as the Kain–Fritsch (KF) cumulus parameterization that has been modified to better represent shallow convective clouds. Testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS). The simulation results are used to investigate the impact of cloud–aerosol interactions on 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 +40% for sulfate under non-precipitating conditions due to sulfate production in the parameterized clouds. The modifications to WRF-Chem are found to account for changes in the cloud droplet number concentration (CDNC) and changes in the chemical composition of cloud droplet residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to the latest version of WRF-Chem, and it

Local and transboundary factors' impacts on trace gases and aerosol during haze episode in 2015 El Niño in Malaysia.

PubMed

Samsuddin, Nur Adilla Che; Khan, Md Firoz; Maulud, Khairul Nizam Abdul; Hamid, Ahmad Hazuwan; Munna, Fahia Tarannum; Rahim, Muhammad Aizat Ab; Latif, Mohd Talib; Akhtaruzzaman, Md

2018-07-15

Southeast Asian haze is a semi-natural phenomenon that chokes the region each year during the dry monsoon season. Smoke-haze episodes caused by the vegetation and peat fires in Indonesia severely affected large parts of Malaysia during the 2015 El Niño phenomenon. This study aimed to evaluate the factors that influenced the concentrations of aerosol and trace gases during the 2015 haze and non-haze period on a semi-urban site in the southern part of Malaysian peninsula that facing Sumatra (Muar, Site A), and on an urban site near to Kuala Lumpur, influenced by the city centre (Cheras, Site B). Local land use data and the cluster of air mass weighted backward trajectory were used to identify the potential factors from local sources and the transboundary region, respectively. The annual median concentrations of PM 10 for semi-urban and urban sites were 45.0μg/m 3 and 47.0μg/m 3 , respectively for the study period (Jan-Dec 2015) from the hourly observation dataset. The highest PM 10 concentrations during the haze were 358μg/m 3 and 415μg/m 3 for the two sites, respectively, representing absolutely unhealthy air. However, the trace gases were within the safe threshold. The average concentrations of PM 10 and carbon monoxide were two fold higher during the haze than the non-haze episodes on both sites. Nitrogen dioxide was more influenced by haze compared with sulphur dioxide and ozone. The results of the land use change suggest that the local factor can also partially affect the air pollution on the urban area (Site B) but more visible in 2015. The results of the backward trajectory and the wildfire radiative power showed that the smoke-haze episodes that affected Malaysia in 2015 were mainly initiated in the Indonesian Sumatra and Kalimantan regions. This study provides a very useful information towards the impacted region during El Niño haze episode. Copyright © 2017 Elsevier B.V. All rights reserved.

A new WRF-Chem treatment for studying regional-scale impacts of cloud processes on aerosol and trace gases in parameterized cumuli

DOE PAGES

Berg, L. K.; Shrivastava, M.; Easter, R. C.; ...

2015-02-24

A new treatment of cloud effects on aerosol and trace gases within parameterized shallow and deep convection, and aerosol effects on cloud droplet number, has been implemented in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) version 3.2.1 that can be used to better understand the aerosol life cycle over regional to synoptic scales. The modifications to the model include treatment of the cloud droplet number 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 convectivemore » cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. These changes have been implemented in both the WRF-Chem chemistry packages as well as the Kain–Fritsch (KF) cumulus parameterization that has been modified to better represent shallow convective clouds. Testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS). The simulation results are used to investigate the impact of cloud–aerosol interactions on 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 +40% for sulfate under non-precipitating conditions due to sulfate production in the parameterized clouds. The modifications to WRF-Chem are found to account for changes in the cloud droplet number concentration (CDNC) and changes in the chemical composition of cloud droplet residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to the latest version of WRF-Chem, and it

Trace gas detection in hyperspectral imagery using the wavelet packet subspace

NASA Astrophysics Data System (ADS)

Salvador, Mark A. Z.

This dissertation describes research into a new remote sensing method to detect trace gases in hyperspectral and ultra-spectral data. This new method is based on the wavelet packet transform. It attempts to improve both the computational tractability and the detection of trace gases in airborne and spaceborne spectral imagery. Atmospheric trace gas research supports various Earth science disciplines to include climatology, vulcanology, pollution monitoring, natural disasters, and intelligence and military applications. Hyperspectral and ultra-spectral data significantly increases the data glut of existing Earth science data sets. Spaceborne spectral data in particular significantly increases spectral resolution while performing daily global collections of the earth. Application of the wavelet packet transform to the spectral space of hyperspectral and ultra-spectral imagery data potentially improves remote sensing detection algorithms. It also facilities the parallelization of these methods for high performance computing. This research seeks two science goals, (1) developing a new spectral imagery detection algorithm, and (2) facilitating the parallelization of trace gas detection in spectral imagery data.

The relation between molecular structure and biological activity among mononitrophenols containing halogens

USGS Publications Warehouse

Applegate, Vernon C.; Johnson, B.G.H.; Smith, Manning A.

1966-01-01

The results of tests of the biological activity of certain nitrophenols containing halogen are reported. Some of these are shown to be significantly more toxic to larvae of the sea lamprey (Petromyzon marinus L.) than to fishes. It is proposed that the death of lamprey larvae exposed to these compounds results from an acute hypotension (shock) with concomitant circulatory and respiratory failure. Rainbow trout (Salmo gairdneri), on the other hand, appear to die, at higher concentrations of the toxin, due to a chemically-caused mechanical interference with respiration through the gills. A systematic series of studies of mononitrophenols containing halogens disclosed that those phenols having the nitro group in the para-position and a halogen atom or group in the meta-position are generally more toxic to lampreys than to fish. The halogens or halogen groups used in this study were fluorine, chlorine, bromine, and trifluormethyl. The same substituents in other positions only occasionally gave rise to selectively toxic compounds. The relationship between the selectively active class of nitrophenols containing halogens and other related structures is discussed.

Measurements of IO in the Tropical Marine Boundary Layer using Laser-Induced Fluorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Walker, H.; Ingham, T.; Heard, D. E.

2012-12-01

Halogenated short-lived substances (VSLS) are emitted from the oceans by marine species such as macroalgae and phytoplankton and contribute to halogen loading in the troposphere and lower stratosphere. Transport of halogenated VSLS into the stratosphere occurs mainly in the tropics, where ascending warm air carries them aloft, and leads to catalytic depletion of stratospheric ozone on a global scale and formation of the Antarctic ozone hole. The tropical marine environment is therefore an important region in which to study the effects of these short-lived halogen species on ozone depletion. The SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project combines ship-borne, aircraft-based and ground-based measurements in and over the South China Sea and the Sulu Sea, and around the coast of Malaysian Borneo, to reduce uncertainties in the amount of halogenated VSLS reaching the stratosphere, the associated ozone depletion, and the effects of a changing climate on these processes. In this work we present measurements of IO radicals made onboard the German research vessel Sonne during SHIVA, between Singapore and Manila. IO is formed via photolysis of iodine-containing source gases (e.g. I2, CH3I) to produce I atoms, which react with ozone. It is therefore an important species to consider when assessing the impacts of halogen chemistry on ozone depletion. Measurements of IO were made over a two-week period by the University of Leeds Laser-Induced Fluorescence (LIF) instrument, which excites IO radicals at λ ~ 445 nm and detects the resultant fluorescence at λ ~ 512 nm. A suite of supporting gas- and aqueous-phase measurements were also made, including concentrations of halocarbons (e.g. CHBr3, CH3I), trace pollutant gases (e.g. CO, O3, NOx), and biological parameters (e.g. abundance and speciation of phytoplankton). Preliminary data analysis indicates that IO was detected above the instrumental limit of detection (0.3 pptv for a 30 minute averaging

Where do California's greenhouse gases come from?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, Marc

2009-12-11

Last March, more than two years after California passed legislation to slash greenhouse gas emissions 25 percent by 2020, Lawrence Berkeley National Laboratory scientist Marc Fischer boarded a Cessna loaded with air monitoring equipment and crisscrossed the skies above Sacramento and the Bay Area. Instruments aboard the aircraft measured a cocktail of greenhouse gases: carbon dioxide from fossil fuel use, methane from livestock and landfills, CO2 from refineries and power plants, traces of nitrous oxide from agriculture and fuel use, and industrially produced other gases like refrigerants. The flight was part of the Airborne Greenhouse Gas Emissions Survey, a collaborationmore » between Berkeley Lab, the National Oceanic and Atmospheric Administration, and the University of California, and UC Davis to pinpoint the sources of greenhouse gases in central California. The survey is intended to improve inventories of the states greenhouse gas emissions, which in turn will help scientists verify the emission reductions mandated by AB-32, the legislation enacted by California in 2006.« less

Understanding Biogenic and Anthropogenic Trace Gas Variations Measured Near Cool, CA in June 2010

NASA Astrophysics Data System (ADS)

Klein, B. Z.; Flowers, B. A.; Gorkowski, K.; Dubey, M. K.; Knighton, W. B.; Floerchinger, C.; Herndon, S. C.; Fast, J. D.; Zaveri, R. A.

2011-12-01

Trace gas signatures produced by forested and urban areas differ greatly. Forested areas are dominated by gases produced during photosynthesis and respiration: CO2 and volatile organic compounds (VOCs) including terpenes and isoprene. Urban areas are heavily influenced by vehicle exhaust emissions and have elevated levels of CO, NOx and aromatic hydrocarbons such as benzene. Ozone is produced as a byproduct of both of these sources; it is produced when NOx from urban areas reacts with either anthropogenic or biogenic hydrocarbons. The Carbonaceous Aerosol and Radiative Effects Study (CARES) campaign was conducted during June 2010, in part to observe the evolution of urban air masses as they mix into rural locations and to better understand anthropogenic-biogenic photochemical interactions. The campaign included two ground-based sampling sites, one in Sacramento, CA (T0) and one downwind, approximately 70km NE, rurally located near Cool, CA (T1). In situ measurements of CO2, CO, O3, NO and multiple different VOCs were performed at the T1 site during the study, and are analyzed here to gain insights into the chemistry and transport of these trace gases. Comparisons between these trace gases coupled with transport modeling is used to delineate biogenic and anthropogenic sources. Additionally, comparisons between trace gases produced predominately by biogenic sources provide valuable information on how meteorology affects their production. Two atmospheric models (HYSPLIT back-trajectories and WRF forecasts) are used to predict transport episodes, where polluted air masses from the Sacramento or more distant San Francisco areas are transported to Cool. The two models display significant overlap for eleven different transport episodes during the study period. Both models also agree on two transport-free multiple-day periods. By examining the periods during which the models are in agreement, we are able to characterize with high certainty the trace gas signatures of local

Advanced Global Atmospheric Gases Experiment (AGAGE)

NASA Technical Reports Server (NTRS)

Prinn, Ronald G.; Kurylo, Michael (Technical Monitor)

2004-01-01

We seek funding from NASA for the third year (2005) of the four-year period January 1, 2003 - December 31, 2006 for continued support of the MIT contributions to the multi-national global atmospheric trace species measurement program entitled Advanced Global Atmospheric Gases Experiment (AGAGE). The case for real-time high-frequency measurement networks like AGAGE is very strong and the observations and their interpretation are widely recognized for their importance to ozone depletion and climate change studies and to verification issues arising from the Montreal Protocol (ozone) and Kyoto Protocol (climate). The proposed AGAGE program is distinguished by its capability to measure over the globe at high frequency almost all of the important species in the Montreal Protocol and almost all of the significant non-CO2 gases in the Kyoto Protocol.

Substituent Effects on the [N-I-N](+) Halogen Bond.

PubMed

Carlsson, Anna-Carin C; Mehmeti, Krenare; Uhrbom, Martin; Karim, Alavi; Bedin, Michele; Puttreddy, Rakesh; Kleinmaier, Roland; Neverov, Alexei A; Nekoueishahraki, Bijan; Gräfenstein, Jürgen; Rissanen, Kari; Erdélyi, Máté

2016-08-10

We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyridine)iodine](+) and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine](+) BF4(-) complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by (15)N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N-I-N](+) halogen bond resulted in >100 ppm (15)N NMR coordination shifts. Substituent effects on the (15)N NMR chemical shift are governed by the π population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N-I-N](+) halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine](+) complexes. An increased electron density of the halogen bond acceptor stabilizes the [N···I···N](+) bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N-I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N-X-N](+) halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen](+)-type synthetic reagents.

Substituent Effects on the [N–I–N]+ Halogen Bond

PubMed Central

2016-01-01

We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond resulted in >100 ppm 15N NMR coordination shifts. Substituent effects on the 15N NMR chemical shift are governed by the π population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N–I–N]+ halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine]+ complexes. An increased electron density of the halogen bond acceptor stabilizes the [N···I···N]+ bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N–I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N–X–N]+ halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen]+-type synthetic reagents. PMID:27265247

Double-chamber electrode for spectrochemical determination of chlorine and other halogens

USGS Publications Warehouse

de Paiva, Azevedo; Specht, A.W.; Harner, R.S.

1954-01-01

A double-chamber, graphite electrode, suitable for d.c. arc determination of halogens by means of the alkaline earth halide bands, is described. An upper chamber holds the alkaline earth compound and an interconnected, lower chamber holds the halogen compound. This arrangement assures that there will be an abundance of alkaline earths in the arc by the time the halogen is volatilized from the lower chamber, and thereby promotes maximum emission of the alkaline earth halide bands. ?? 1954.

Characteristics of aerosol particles and trace gases in ship exhaust plumes

NASA Astrophysics Data System (ADS)

Drewnick, F.; Diesch, J.; Borrmann, S.

2011-12-01

Gaseous and particulate matter from marine vessels gain increasing attention due to their significant contribution to the anthropogenic burden of the atmosphere, implying the change of the atmospheric composition and the impact on local and regional air quality and climate (Eyring et al., 2010). As ship emissions significantly affect air quality of onshore regions, this study deals with various aspects of gas and particulate plumes from marine traffic measured near the Elbe river mouth in northern Germany. In addition to a detailed investigation of the chemical and physical particle properties from different types of commercial marine vessels, we will focus on the chemistry of ship plumes and their changes while undergoing atmospheric processing. Measurements of the ambient aerosol, various trace gases and meteorological parameters using a mobile laboratory (MoLa) were performed on the banks of the Lower Elbe which is passed on average, daily by 30 ocean-going vessels reaching the port of Hamburg, the second largest freight port of Europe. During 5 days of sampling from April 25-30, 2011 170 commercial marine vessels were probed at a distance of about 1.5-2 km with high temporal resolution. Mass concentrations in PM1, PM2.5 and PM10 and number as well as PAH and black carbon (BC) concentrations in PM1 were measured; size distribution instruments covered the size range from 6 nm up to 32 μm. The chemical composition of the non-refractory aerosol in the submicron range was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS). Gas phase species analyzers monitored various trace gas concentrations in the air and a weather station provided meteorological parameters. Additionally, a wide spectrum of ship information for each vessel including speed, size, vessel type, fuel type, gross tonnage and engine power was recorded via Automatic Identification System (AIS) broadcasts. Although commercial marine vessels powered by diesel engines consume high

Halogen radicals contribute to photooxidation in coastal and estuarine waters

PubMed Central

Parker, Kimberly M.; Mitch, William A.

2016-01-01

Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl− and Br− by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

Field Measurements of Trace Gases and Aerosols Emitted by Undersampled Combustion Sources Including Wood and Dung Cooking Fires, Garbage and Crop Residue Burning, and Indonesian Peat Fires

NASA Astrophysics Data System (ADS)

Stockwell, C.; Jayarathne, T. S.; Goetz, D.; Simpson, I. J.; Selimovic, V.; Bhave, P.; Blake, D. R.; Cochrane, M. A.; Ryan, K. C.; Putra, E. I.; Saharjo, B.; Stone, E. A.; DeCarlo, P. F.; Yokelson, R. J.

2017-12-01

Field measurements were conducted in Nepal and in the Indonesian province of Central Kalimantan to improve characterization of trace gases and aerosols emitted by undersampled combustion sources. The sources targeted included cooking with a variety of stoves, garbage burning, crop residue burning, and authentic peat fires. Trace gas and aerosol emissions were studied using a land-based Fourier transform infrared spectrometer, whole air sampling, photoacoustic extinctiometers (405 and 870nm), and filter samples that were analyzed off-line. These measurements were used to calculate fuel-based emission factors (EFs) for up to 90 gases, PM2.5, and PM2.5 constituents. The aerosol optical data measured included EFs for the scattering and absorption coefficients, the single scattering albedo (at 870 and 405 nm), as well as the absorption Ångström exponent. The emissions varied significantly by source, although light absorption by both brown and black carbon (BrC and BC, respectively) was important for all non-peat sources. For authentic peat combustion, the emissions of BC were negligible and absorption was dominated by organic aerosol. The field results from peat burning were in reasonable agreement with recent lab measurements of smoldering Kalimantan peat and compare well to the limited data available from other field studies. The EFs can be used with estimates of fuel consumption to improve regional emissions inventories and assessments of the climate and health impacts of these undersampled sources.

Mass spectrometer characterization of halogen gases in air at atmospheric pressure.

PubMed

Ivey, Michelle M; Foster, Krishna L

2005-03-01

We have developed a new interface for a commercial ion trap mass spectrometer equipped with APCI capable of real-time measurements of gaseous compounds with limits of detection on the order of pptv. The new interface has been tested using the detection of Br2 and Cl2 over synthetic seawater ice at atmospheric pressure as a model system. A mechanical pump is used to draw gaseous mixtures through a glass manifold into the corona discharge area, where the molecules are ionized. Analysis of bromine and chlorine in dry air show that ion intensity is affected by the pumping rate and the position of the glass manifold. The mass spectrometer signals for Br2 are linear in the 0.1-10.6 ppbv range, and the estimated 3sigma detection limit is 20 pptv. The MS signals for Cl2 are linear in the 0.2-25 ppbv range, and the estimated 3sigma detection limit is 1 ppbv. This new interface advances the field of analytical chemistry by introducing a practical modification to a commercially available ion trap mass spectrometer that expands the available methods for performing highly specific and sensitive measurements of gases in air at atmospheric pressure.

Toward hydrogen detection at room temperature with printed ZnO nanoceramics films activated with halogen lighting

NASA Astrophysics Data System (ADS)

Nguyen, Van Son; Jubera, Véronique; Garcia, Alain; Debéda, Hélène

2015-12-01

Though semiconducting properties of ZnO have been extensively investigated under hazardous gases, research is still necessary for low-cost sensors working at room temperature. Study of printed ZnO nanopowders-based sensors has been undertaken for hydrogen detection. A ZnO paste made with commercial nanopowders is deposited onto interdigitated Pt electrodes and sintered at 400 °C. The ZnO layer structure and morphology are first examined by XRD, SEM, AFM and emission/excitation spectra prior to the study of the effect of UV-light on the electrical conduction of the semiconductor oxide. The response to hydrogen exposure is subsequently examined, showing that low UV-light provided by halogen lighting enhances the gas response and allows detection at room temperature with gas responses similar to those obtained in dark conditions at 150 °C. A gas response of 44% (relative change in current) under 300 ppm is obtained at room temperature. Moreover, it is demonstrated that very low UV-light power (15 μW/mm2) provided by the halogen lamp is sufficient to give sensitivities as high as those for much higher powers obtained with a UV LED (7.7 mW/mm2). These results are comparable to those obtained by others for 1D or 2D ZnO nanostructures working at room temperature or at temperatures up to 250 °C.

Halogenation of cobalt dicarbollide

DOEpatents

Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

1997-01-01

A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

Balloon-borne photoionization mass spectrometer for measurement of stratospheric gases

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Maier, E. J. R.

1978-01-01

A balloon-borne photoionization mass spectrometer used to measure stratospheric trace gases is described. Ions are created with photons from high-intensity krypton discharge lamps and a quadrupole mass analyzer is employed for ion identification. Differential pumping is achieved with liquid helium cryopumping. To insure measurement of unperturbed stratospheric air, the entire system is contained in a sealed gondola and the atmospheric sample is taken some distance away during descent. The photoionization technique allows the detection of a low ionization potential constituent, such as nitric oxide, at less than a part in one billion in the presence of the major atmospheric gases and their isotopes. Operation of the mass spectrometer system was demonstrated during a daytime flight from Palestine, Texas on 26 April 1977. The sensitivity achieved and the unique selectivity afforded by this technique offer a capability for trace constituent measurement not possible with the more conventional electron impact ionization approach.

Preparation and analysis of zero gases for the measurement of trace VOCs in air monitoring

NASA Astrophysics Data System (ADS)

Englert, Jennifer; Claude, Anja; Demichelis, Alessia; Persijn, Stefan; Baldan, Annarita; Li, Jianrong; Plass-Duelmer, Christian; Michl, Katja; Tensing, Erasmus; Wortman, Rina; Ghorafi, Yousra; Lecuna, Maricarmen; Sassi, Guido; Sassi, Maria Paola; Kubistin, Dagmar

2018-06-01

Air quality observations are performed globally to monitor the status of the atmosphere and its level of pollution and to assess mitigation strategies. Regulations of air quality monitoring programmes in various countries demand high-precision measurements for harmful substances often at low trace concentrations. These requirements can only be achieved by using high-quality calibration gases including high-purity zero gas. For volatile organic compound (VOC) observations, zero gas is defined as being hydrocarbon-free and can be, for example, purified air, nitrogen or helium. It is essential for the characterisation of the measurement devices and procedures, for instrument operation as well as for calibrations. Two commercial and one self-built gas purifiers were tested for their VOC removal efficiency following a standardised procedure. The tested gas purifiers included one adsorption cartridge with an inorganic media and two types of metal catalysts. A large range of VOCs were investigated, including the most abundant species typically measured at air monitoring stations. Both catalysts were able to remove a large range of VOCs whilst the tested adsorption cartridge was not suitable to remove light compounds up to C4. Memory effects occurred for the adsorption cartridge when exposed to higher concentration. This study emphasises the importance of explicitly examining a gas purifier for its intended application before applying it in the field.

Climate change and trace gases.

PubMed

Hansen, James; Sato, Makiko; Kharecha, Pushker; Russell, Gary; Lea, David W; Siddall, Mark

2007-07-15

Palaeoclimate data show that the Earth's climate is remarkably sensitive to global forcings. Positive feedbacks predominate. This allows the entire planet to be whipsawed between climate states. One feedback, the 'albedo flip' property of ice/water, provides a powerful trigger mechanism. A climate forcing that 'flips' the albedo of a sufficient portion of an ice sheet can spark a cataclysm. Inertia of ice sheet and ocean provides only moderate delay to ice sheet disintegration and a burst of added global warming. Recent greenhouse gas (GHG) emissions place the Earth perilously close to dramatic climate change that could run out of our control, with great dangers for humans and other creatures. Carbon dioxide (CO2) is the largest human-made climate forcing, but other trace constituents are also important. Only intense simultaneous efforts to slow CO2 emissions and reduce non-CO2 forcings can keep climate within or near the range of the past million years. The most important of the non-CO2 forcings is methane (CH4), as it causes the second largest human-made GHG climate forcing and is the principal cause of increased tropospheric ozone (O3), which is the third largest GHG forcing. Nitrous oxide (N2O) should also be a focus of climate mitigation efforts. Black carbon ('black soot') has a high global warming potential (approx. 2000, 500 and 200 for 20, 100 and 500 years, respectively) and deserves greater attention. Some forcings are especially effective at high latitudes, so concerted efforts to reduce their emissions could preserve Arctic ice, while also having major benefits for human health, agricultural productivity and the global environment.

Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

DOEpatents

Goodman, Mark M.; Faraj, Bahjat

1999-01-01

Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

DOEpatents

Goodman, M.M.; Faraj, B.

1999-07-06

Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

RESIDUAL RISK ASSESSMENT: HALOGENATED SOLVENTS

EPA Science Inventory

This source category previously subjected to a technology-based standard will be examined to determine if health or ecological risks are significant enough to warrant further regulation for Halogenated Solvent Degreasing Facilities. These assessments utilize existing models and d...

Polar Vortex Dynamics During Spring and Fall Diagnosed Using ATMOS Trace Gas Observation

NASA Technical Reports Server (NTRS)

Manney, G.; Michelsen, H.; Santee, M.; Gunson, M.; Irion, F.; Roche, A.; Livesey, N.

1999-01-01

Trace gases measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during the Mar/Apr 1992(AT-1), Apr 1993(AT-2), and Nov 1994(AT-3) space-shuttle missions have been mapped into equivalent latitude/potential temperature (EqL/0) coordinates.

Reduction of halogenated ethanes by green rust.

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Loughlin, E. J.; Burris, D. R.; Environmental Research

Green rusts, mixed Fe{sup II}/Fe{sup III} hydroxide minerals present in many suboxic environments, have been shown to reduce a number of organic and inorganic contaminants. The reduction of halogenated ethanes was examined in aqueous suspensions of green rust, both alone and with the addition of Ag{sup I} (AgGR) and Cu{sup II} (CuGR). Hexachloroethane (HCA), pentachloroethane (PCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA), and 1,2-dibromoethane were reduced in the presence of green rust alone, AgGR, or CuGR; only 1,2-dichloroethane and chloroethane were nonreactive. The reduction was generally more rapid for more highly substituted ethanes than for ethanesmore » having fewer halogen groups (HCA > PCA > 1,1,1,2-TeCA > 1,1,1-TCA > 1,1,2,2-TeCA > 1,1,2-TCA > 1,1-DCA), and isomers with the more asymmetric distributions of halogen groups were more rapidly reduced than the isomer with greater symmetry (e.g., 1,1,1-TCA > 1,1,2-TCA). The addition of Ag{sup I} or Cu{sup II} to green rust suspensions resulted in a substantial increase in the rate of halogenated ethane reduction as well as significant differences in the product distributions with respect to green rust alone.« less

Differential Radiometers Using Fabry-Perot Interferometric Technique for Remote Sensing Determination of Various Atmospheric Trace Gases

NASA Technical Reports Server (NTRS)

Georgieva, E. M.; Heaps, W. S.; Wilson, E. L.

2007-01-01

New type of remote sensing instrument based upon the Fabry-Perot inte rferometric technique has been developed at NASA's Goddard Space Flight Center. Fabry-Perot interferometry (FPI) is a well known, powerful spectroscopic technique and one of its many applications is to be use d to measure greenhouse gases and also some harmful species in the at mosphere. With this technique, absorption of particular species is me asured and related to its concentration. A solid Fabry-Perot etalon is used as a frequency filter to restrict the measurement to particular absorption bands of the gas of interest. With adjusting the thicknes s of the etalon that separation (in frequency) of the transmitted fri nges can be made equal to the almost constant separation of the gas a bsorption lines. By adjusting the temperature of the etalon, which changes the index of refi-action of its material, the transmission fring es can be brought into nearly exact correspondence with absorption li nes of the particular species. With this alignment between absorption lines and fringes, changes in the amount of a species in the atmosph ere strongly affect the amount of light transmitted by the etalon and can be related to gas concentration. The instrument that we have dev eloped detects the absorption of various atmospheric trace gases in d irect or reflected sunlight. Our instrument employing Fabry-Perot interferometer makes use of two features to achieve high sensitivity. The first is high spectral resolution enabling one to match the width of an atmospheric absorption feature by the instrumental band pass. The second is high optical throughput enabled by using multiple spectral lines simultaneously. For any species that one wishes to measure, thi s first feature is available while the use of multiple spectral features can be employed only for species with suitable spectra and freedom from interfering species in the same wavelength region. We have deve loped an instrument for use as ground based

Binding interactions of halogenated bisphenol A with mouse PPARα: In vitro investigation and molecular dynamics simulation.

PubMed

Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Guan, Tianzhu; Yu, Hansong; Li, Zhuolin; Wang, Yongzhi; Wang, Yongjun; Zhang, Tiehua

2018-02-01

The binding of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to mouse peroxisome proliferator-activated receptor α ligand binding domain (mPPARα-LBD) was examined by a combination of in vitro investigation and in silico simulation. Fluorescence polarization (FP) assay showed that halogenated BPAs could bind to mPPARα-LBD* as the affinity ligands. The calculated electrostatic potential (ESP) illustrated the different charge distributions of halogenated BPAs with altered halogenation patterns. As electron-attracting substituents, halogens decrease the positive electrostatic potential and thereby have a significant influence on the electrostatic interactions of halogenated BPAs with mPPARα-LBD*. The docking results elucidated that hydrophobic and hydrogen-bonding interactions may also contribute to stabilize the binding of the halogenated BPAs to their receptor molecule. Comparison of the calculated binding energies with the experimentally determined affinities yielded a good correlation (R 2 =0.6659) that could provide a rational basis for designing environmentally benign chemicals with reduced toxicities. This work can potentially be used for preliminary screening of halogenated BPAs. Copyright © 2017 Elsevier B.V. All rights reserved.

Halogenation of cobalt dicarbollide

DOEpatents

Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

1997-05-20

A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

Investigation of reactive halogens in the Arctic using a mobile instrumental laboratory

NASA Astrophysics Data System (ADS)

Custard, K.; Shepson, P. B.; Stephens, C. R.

2011-12-01

Custard, K kcustard@purdue.edu Chemistry Department, Purdue University, West Lafayette, IN, USA Shepson, P pshepson@purdue.edu Chemistry Department, Purdue University, West Lafayette, IN, USA Stephens, C thompscr@purdue.edu Chemistry Department, Purdue University, West Lafayette, IN, USA Investigation of the chemistry of reactive halogens in ice-covered regions is important because of its significant impact on atmospheric composition. Halogens in the Arctic react with ozone and gaseous elemental mercury to sometimes completely deplete them from the ambient atmosphere, at least during polar springtime. There is much uncertainty about the sources and concentrations of these atmospheric halogens in the Arctic, particularly with respect to chlorine. To gain a better understanding of them, we have developed a method to simultaneously measure the concentrations of BrOx and ClOx radicals using a flowtube method. The method involves reaction of the halogen atom with a halogenated alkene, to produce a multiply halogenated characteristic ketone product, which is then detected via GC/ECD. The system was deployed at Barrow, AK, using a mobile instrumental laboratory so that measurements could be made from multiple locations along the sea ice. In this paper we will discuss laboratory evaluation of the flowtube method, and present preliminary data from Barrow, AK, during the spring 2011 deployment.

Trace Gases - A Warning Signs of Impending Major Seismic Activity

NASA Astrophysics Data System (ADS)

Baijnath, J.; Freund, F.; Li, J.

2013-12-01

isopropanol and with a highly reduced butyn containing triple-bonded C and an aromatic ring were used. Multiple tests were conducted to study the interaction of stressed-activated positive hole charge carriers with organic versus inorganic and dry versus moist materials. This study suggests that the appearance of certain trace gases may be useful as a pre-earthquake indicator.

Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

NASA Astrophysics Data System (ADS)

Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli

2018-03-01

The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartocci, Alessio; Cappelletti, David; Pirani, Fernando

2015-05-14

The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl{sub 4} and CF{sub 4}. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypicalmore » Ng-CCl{sub 4} and Ng-CF{sub 4} and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF{sub 4}, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl{sub 4}, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential

Trace gas emissions from burning Florida wetlands

NASA Astrophysics Data System (ADS)

Cofer, Wesley R.; Levine, Joel S.; Winstead, Edward L.; Lebel, Peter J.; Koller, Albert M.; Hinkle, C. Ross

1990-02-01

Measurements of biomass burn-produced trace gases are presented that were obtained using a helicopter at low altitudes above burning Florida wetlands on November 9, 1987, and from both helicopter and light-aircraft samplings on November 7, 1988. Carbon dioxide (CO2) normalized emission ratios (ΔX/ΔCO2; V/V; where X is trace gas) for carbon monoxide (CO), hydrogen (H2), methane (CH4), total nonmethane hydrocarbons (TNMHC), and nitrous oxide (N2O) were obtained over burning graminoid wetlands consisting primarily of Spartina bakeri and Juncus roemerianus. Some interspersed scrub oak (Quercus spp) and saw palmetto (Screnoa repens) were also burned. No significant differences were observed in the emission ratios determined for these gases from samples collected over flaming, mixed, and smoldering phases of combustion during the 1987 fire. Combustion-categorized differences in emission ratios were small for the 1988 fire. Combustion efficiency was relatively good (low emission ratios for reduced gases) for both fires. We believe that the consistently low emission ratios were a unique result of graminoid wetlands fires, in which the grasses and rushes (both small-size fuels) burned rapidly down to standing water and were quickly extinguished. Consequently, the efficiency of the combustion was good and the amount and duration of smoldering combustion was greatly diminished.

Fine tuning of graphene properties by modification with aryl halogens

NASA Astrophysics Data System (ADS)

Bouša, D.; Pumera, M.; Sedmidubský, D.; Šturala, J.; Luxa, J.; Mazánek, V.; Sofer, Z.

2016-01-01

Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06295k

Halogen-free benzoxazine based curable compositions for high TG applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tietze, Roger; Nguyen, Yen-Loan

The present invention provides a halogen-free curable composition including a benzoxazine monomer, at least one epoxy resin, a catalyst, a toughening agent and a solvent. The halogen-free curable composition is especially suited for use in automobile and aerospace applications since the composition, upon curing, produces a composite having a high glass transition temperature.

CHAiOS: Chemistry of Halogens at the Isles of Shoals

NASA Astrophysics Data System (ADS)

Keene, W. C.; Stutz, J.; Pszenny, A. A.; Russell, L.; von Glasow, R.; Sive, B.; Varner, R.

2005-12-01

During summer 2004, a comprehensive suite of reactive trace gases (including halogen radicals and precursors, O3, reactive N, soluble acids, NH3, HCHO, SO2, hydrocarbons, and halocarbons), the chemical and physical characteristics of size-resolved aerosols, actinic flux, and related physical conditions was measured at Appledore Island, ME as part of the International Consortium for Atmospheric Research on Transport and Transformations (ICARTT). Acid displacement of sea-salt Cl- primarily by HNO3 sustained high HCl mixing ratios (often >2000 pptv or >5 * 1010 cm-3) during daytime. HCl + OH produced 105 to 106 Cl atoms cm-3 sec-1. Cl* (including HOCl and Cl2) typically ranged from <20 (<5 * 108 cm-3) to about 100 pptv (3 * 109 cm-3). Depending on its assumed composition, Cl* photolysis yielded an additional source for Cl ranging from <104 to 107 atoms cm-3 sec-1. Maximum steady-state Cl concentrations during daytime (104 to 106 atoms cm-3) indicated significant contributions to oxidizing capacity. IO, OIO, and I2 were quantified simultaneously by long-path and MAX DOAS. IO ranged from <1.8 to 7 pptv, was detected only during daytime at wind speeds >2 m sec-1, and was uncorrelated with tidal height. For the first time, OIO was detected during daytime indicating that photolysis was an unimportant sink. The presence of OIO at high NOx implies unknown chemical pathways. Calculations with the 1-D photochemical model MISTRA predict longer lifetimes for OIO relative to IO, consistent with observations. I chemistry influenced ozone significantly by direct reaction (e.g., I + O3 → IO + O2) and by changing OH/HO2 and NO/NO2 ratios. Aerosols in all size fractions were highly enriched in I relative to sea salt (factors of 102 to 105) indicating active multiphase transformations. Numerous aerosol growth events were detected some of which were associated with elevated IO and OIO. However, the lack of consistent correlation with iodine species suggests that I chemistry may not be

Spatiotemporal Patterns of Urban Trace Gases and Pollutants Observed with a Light Rail Vehicle Platform in Salt Lake City, UT

NASA Astrophysics Data System (ADS)

Mitchell, L.; Crosman, E.; Fasoli, B.; Leclair-Marzolf, L.; Jacques, A.; Horel, J.; Lin, J. C.; Bowling, D. R.; Ehleringer, J. R.

2015-12-01

Urban environments are characterized by both spatial complexity and temporal variability, each of which present challenges for measurement strategies aimed at constraining estimates of greenhouse gas emissions and air quality. To address these challenges we initiated a project in December 2014 to measure trace species (CO2, CH4, O3, and Particulate Matter) by way of a Utah Transit Authority (UTA) light rail vehicle whose route traverses the Salt Lake Valley in Utah on an hourly basis, retracing the same route through commercial, residential, suburban, and rural typologies. Light rail vehicles present advantages as a measurement platform, including the absence of in-situ fossil fuel emissions, repeated transects across a urban region that provides both spatial and temporal information, and relatively low operating costs. We present initial results from the first year of operations including the spatiotemporal patterns of greenhouse gases and pollutants across Salt Lake City, UT with an emphasis on criteria pollutants, identification of sources, and future applications of this measurement platform.

Halogen bonding (X-bonding): A biological perspective

PubMed Central

Scholfield, Matthew R; Zanden, Crystal M Vander; Carter, Megan; Ho, P Shing

2013-01-01

The concept of the halogen bond (or X-bond) has become recognized as contributing significantly to the specificity in recognition of a large class of halogenated compounds. The interaction is most easily understood as primarily an electrostatically driven molecular interaction, where an electropositive crown, or σ-hole, serves as a Lewis acid to attract a variety of electron-rich Lewis bases, in analogous fashion to a classic hydrogen bonding (H-bond) interaction. We present here a broad overview of X-bonds from the perspective of a biologist who may not be familiar with this recently rediscovered class of interactions and, consequently, may be interested in how they can be applied as a highly directional and specific component of the molecular toolbox. This overview includes a discussion for where X-bonds are found in biomolecular structures, and how their structure–energy relationships are studied experimentally and modeled computationally. In total, our understanding of these basic concepts will allow X-bonds to be incorporated into strategies for the rational design of new halogenated inhibitors against biomolecular targets or toward molecular engineering of new biological-based materials. PMID:23225628

The Analysis of PPM Levels of Gases in Air by Photoionization Mass Spectrometry

ERIC Educational Resources Information Center

Driscoll, John N.; Warneck, Peter

1973-01-01

Discusses analysis of trace gases in air by photoionization mass spectrometer. It is shown that the necessary sensitivity can be obtained by eliminating the UV monochromator and using direct ionization with a hydrogen light source. (JP)

Process for oxidation of hydrogen halides to elemental halogens

DOEpatents

Lyke, Stephen E.

1992-01-01

An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

Recent trends of inorganic chlorine and halogenated source gases above the Jungfraujoch and Kitt Peak stations derived from high-resolution FTIR solar observations

NASA Astrophysics Data System (ADS)

Mahieu, Emmanuel; Rinsland, Curtis P.; Gardiner, Tom; Zander, Rodolphe; Demoulin, Philippe; Chipperfield, Martyn P.; Ruhnke, Roland; Chiou, Linda S.; de Mazière, Martine

2010-05-01

The longest series of Fourier Transform Infrared (FTIR) high spectral resolution solar absorption observations are available from the Jungfraujoch and Kitt Peak stations, located at 46.5°N and 30.9°N, respectively. State-of-the-art interferometers are operated at these sites within the framework of the Network for the Detection of Atmospheric Composition Change (NDACC, visit http://www.ndacc.org). These instruments allow to record spectra on a regular basis, under clear-sky conditions, using a suite of optical filters which altogether cover the 2 to 16 micron spectral range. Numerous absorption features characterized in the HITRAN compilations (e.g. Rothman et al., 2008) are encompassed in this mid-infrared region. Their analyses with either the SFIT-1 or SFIT-2 algorithm allow retrieving total columns of the target gases. Moreover, information on their distribution with altitude can generally be derived when using SFIT-2 which implements the Optimal Estimation Method of Rodgers (1990). Among the two dozen gases of atmospheric interest accessible to the ground-based FTIR technique, we have selected here a suite of long-lived halogenated species: HCl, ClONO2, CCl2F2, CCl3F, CHClF2, CCl4 and SF6. Time series available from the two sites will be presented, compared and critically discussed. In particular, changes in the abundances of theses gases since the peak in inorganic chlorine (Cly, which occurred in 1996-1997) and their intra-annual variability will be characterized with a statistical tool using bootstrap resampling (Gardiner et al., 2008). Trends and their associated uncertainties will be reported and put into perspective with the phase-out regulations of the production of ozone depleting substances adopted and implemented by the Montreal Protocol, its Amendments and Adjustments. For instance, the trends affecting the reservoir species HCl, ClONO2, and their summation which is a good proxy of the total inorganic chlorine, have been calculated using all

Metagenomic evidence for metabolism of trace atmospheric gases by high-elevation desert Actinobacteria

PubMed Central

Lynch, Ryan C.; Darcy, John L.; Kane, Nolan C.; Nemergut, Diana R.; Schmidt, Steve K.

2014-01-01

Previous surveys of very dry Atacama Desert mineral soils have consistently revealed sparse communities of non-photosynthetic microbes. The functional nature of these microorganisms remains debatable given the harshness of the environment and low levels of biomass and diversity. The aim of this study was to gain an understanding of the phylogenetic community structure and metabolic potential of a low-diversity mineral soil metagenome that was collected from a high-elevation Atacama Desert volcano debris field. We pooled DNA extractions from over 15 g of volcanic material, and using whole genome shotgun sequencing, observed only 75–78 total 16S rRNA gene OTUs3%. The phylogenetic structure of this community is significantly under dispersed, with actinobacterial lineages making up 97.9–98.6% of the 16S rRNA genes, suggesting a high degree of environmental selection. Due to this low diversity and uneven community composition, we assembled and analyzed the metabolic pathways of the most abundant genome, a Pseudonocardia sp. (56–72% of total 16S genes). Our assembly and binning efforts yielded almost 4.9 Mb of Pseudonocardia sp. contigs, which accounts for an estimated 99.3% of its non-repetitive genomic content. This genome contains a limited array of carbohydrate catabolic pathways, but encodes for CO2 fixation via the Calvin cycle. The genome also encodes complete pathways for the catabolism of various trace gases (H2, CO and several organic C1 compounds) and the assimilation of ammonia and nitrate. We compared genomic content among related Pseudonocardia spp. and estimated rates of non-synonymous and synonymous nucleic acid substitutions between protein coding homologs. Collectively, these comparative analyses suggest that the community structure and various functional genes have undergone strong selection in the nutrient poor desert mineral soils and high-elevation atmospheric conditions. PMID:25566214

First results of the observations of trace gases in the Martian atmosphere by the Planetary Fourier Spectrometer onboard the Mars Express

NASA Astrophysics Data System (ADS)

Titov, D. V.; Ignatiev, N.; Formisano, V.; Grassi, D.; Giuranna, M.; Maturilli, A.; Piccioni, G.; Moroz, V. I.; Lellouch, E.; Encrenaz, T.; Pfs Team

High spectral resolution observations of Mars by the PFS/Mars Express provide new insight into the atmospheric composition. Spectral features of atmospheric CO2 and its isotopes at 15, 4.3, 2.7, 1.4 μ m, CO at 4.7 and 2.35 μ m, and H2O at 40, 2.56, and 1.38 μ m as well as solar spectral features are clearly identified in the PFS spectra. HDO spectral details at 3.7 μ m were also tentatively detected. The paper will present qualitative and quantitative analysis of the PFS spectra in the regions of spectral bands of trace gases. Abundance of minor constituents will be determined using complete radiative transfer modeling including possible non-LTE effects. We will also present results of search for other minor species with emphasis on the limb observations that provide higher air mass factor.

A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil

PubMed Central

Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H.; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

2016-01-01

In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications. PMID:27353292

Density functional IR, Raman, and VCD spectra of halogen substituted β-lactams

NASA Astrophysics Data System (ADS)

Rode, Joanna E.; Dobrowolski, Jan Cz.

2003-06-01

Halogenoazetidinones are important as synthetic intermediates for preparation of halogen β-lactam (2-azetidinone) antibiotics and as building blocks for carbohydrates and amino acids. In this paper, we consider the influence of the halogen atom, substituted at the C4 position of the 2-azetidinone ring, on the geometry, IR, Raman, and vibrational circular dichroism spectra. The vibrational spectra were calculated for the chiral 4-( R)-X-2-azetidinone (X=F, Cl or Br) molecules at the B3PW91/aug-cc-pVTZ level. It was shown that the geometry of the molecules studied do not change much upon the change of the halogen atom. In case of the vibrational spectra, the position but even more the intensities depend strongly on the kind of halogen substituent.

A Comparison of Aircraft and Ground-Based Measurements at Mauna Loa Observatory, Hawaii, During GTE PEM-West and MLOPEX 2

NASA Technical Reports Server (NTRS)

Atlas, E.; Ridley, B.; Walega, J.; Greenberg, J.; Kok, G.; Staffelbach, T.; Schauffler, S.; Lind, J.; Huebler, G.; Norton, R.

1996-01-01

During October 19-20, 1991, one flight of the NASA Global Tropospheric Experiment (GTE) Pacific Exploratory Mission (PEM-West A) mission was conducted near Hawaii as an intercomparison with ground-based measurements of the Mauna Loa Observatory Photochemistry Experiment (MLOPEX 2) and the NOAA Climate Modeling and Diagnostics Laboratory (CMDL). Ozone, reactive nitrogen species, peroxides, hydrocarbons, and halogenated hydrocarbons were measured by investigators aboard the DC-8 aircraft and at the ground site. Lidar cross sections of ozone revealed a complex air mass structure near the island of Hawaii which was evidenced by large variation in some trace gas mixing ratios. This variation limited the time and spatial scales for direct measurement intercomparisons. Where differences occurred between measurements in the same air masses, the intercomparison suggested that biases for some trace gases was due to different calibration scales or, in some cases, instrumental or sampling biases. Relatively large uncertainties were associated with those trace gases present in the low parts per trillion by volume range. Trace gas correlations were used to expand the scope of the intercomparison to identify consistent trends between the different data sets.

Inland Sea Spray Aerosol Transport and Incomplete Chloride Depletion: Varying Degrees of Reactive Processing Observed during SOAS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bondy, Amy L.; Wang, Bingbing; Laskin, Alexander

Multiphase reactions involving sea spray aerosol (SSA) impact trace gases budgets in coastal regions by acting as a reservoir for oxidized nitrogen and sulfur species, as well as a source of halogen gases (HCl, ClNO2, etc.). While most studies of multiphase reactions on SSA have focused on marine environments, far less is known about SSA transported inland. Herein, single particle measurements of SSA are reported at a site > 320 km from the Gulf of Mexico, with transport times of 7-68 h. Samples were collected during the Southern Oxidant and Aerosol Study (SOAS) in June-July 2013 near Centreville, Alabama. SSAmore » was observed in 93% of 42 time periods analyzed. During two marine air mass periods, SSA represented significant number fractions of particles in the accumulation (0.2-1.0 μm, 11%) and coarse (1.0-10.0 μm, 35%) modes. Chloride content of SSA particles ranged from full to partial depletion, with 24% of SSA particles containing chloride (mole fraction of Cl/Na > 0.1, 90% chloride depletion). Both the frequent observation of SSA at an inland site and the range of chloride depletion observed, suggest that SSA may represent an underappreciated inland sink for NOx/SO2 and source of halogen gases.« less

Interpretation of Trace Gas Data Using Inverse Methods and Global Chemical Transport Models

NASA Technical Reports Server (NTRS)

Prinn, Ronald G.

1997-01-01

This is a theoretical research project aimed at: (1) development, testing, and refining of inverse methods for determining regional and global transient source and sink strengths for long lived gases important in ozone depletion and climate forcing, (2) utilization of inverse methods to determine these source/sink strengths which use the NCAR/Boulder CCM2-T42 3-D model and a global 3-D Model for Atmospheric Transport and Chemistry (MATCH) which is based on analyzed observed wind fields (developed in collaboration by MIT and NCAR/Boulder), (3) determination of global (and perhaps regional) average hydroxyl radical concentrations using inverse methods with multiple titrating gases, and, (4) computation of the lifetimes and spatially resolved destruction rates of trace gases using 3-D models. Important goals include determination of regional source strengths of methane, nitrous oxide, and other climatically and chemically important biogenic trace gases and also of halocarbons restricted by the Montreal Protocol and its follow-on agreements and hydrohalocarbons used as alternatives to the restricted halocarbons.

The ice record of greenhouse gases: a view in the context of future changes

NASA Astrophysics Data System (ADS)

Raynaud, D.; Barnola, J.-M.; Chappellaz, J.; Blunier, T.; Indermühle, A.; Stauffer, B.

2000-01-01

Analysis of air trapped in polar ice provides the most direct information on the natural variability of Greenhouse Trace Gases (GTG). It gives the context for the dramatic change in their atmospheric concentrations induced by anthropogenic activities over the last 200 yr, leading to present-day levels which have been unprecedented over the last 400,000 yr. The GTG ice record also provides insight into the processes generally involved in the interplay between these trace gases and the climate and in particular those which are likely to take place in the next centuries in terms of climate changes and climate feedbacks on ecosystems. The paper gives selected examples of the GTG record, taken during different climatic periods in the past, and illustrating what we can learn in terms of processes.

Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

PubMed

Barón, E; Hauler, C; Gallistl, C; Giménez, J; Gauffier, P; Castillo, J J; Fernández-Maldonado, C; de Stephanis, R; Vetter, W; Eljarrat, E; Barceló, D

2015-08-04

Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.

Sorption of halogenated phenols and pharmaceuticals to biochar: affecting factors and mechanisms.

PubMed

Oh, Seok-Young; Seo, Yong-Deuk

2016-01-01

The feasibility of using biochar as a sorbent to remove nine halogenated phenols (2,4-dichlorophenol, 2,4-dibromophenol, 2,4-difluorophenol, 2-chlorophenol, 4-chlorophenol, 2-bromophenol, 4-bromophenol, 2-fluorophenol, and 4-fluorophenol) and two pharmaceuticals (triclosan and ibuprofen) from water was examined through a series of batch experiments. Types of biochar, synthesized using various biomasses including fallen leaves, rice straw, corn stalk, used coffee grounds, and biosolids, were evaluated. Compared to granular activated carbon (GAC), most of the biochar samples did not effectively remove halogenated phenols or pharmaceuticals from water. The increase in pH and deprotonation of phenols in biochar systems may be responsible for its ineffectiveness at this task. When pH was maintained at 4 or 7, the sorption capacity of biochar was markedly increased. Considering maximum sorption capacity and properties of sorbents and sorbates, it appears that the sorption capacity of biochar for halogenated phenols is related to the surface area and carbon content of the biochar and the hydrophobicity of halogenated phenols. In the cases of triclosan and ibuprofen, the sorptive capacities of GAC, graphite, and biochars were also significantly affected by pH, according to the point of zero charge (PZC) of sorbents and deprotonation of the pharmaceuticals. Pyrolysis temperature did not affect the sorption capacity of halogenated phenols or pharmaceuticals. Based on the experimental observations, some biochars are good candidates for removal of halogenated phenols, triclosan, and ibuprofen from water and soil.

Temporal dynamics of halogenated organic compounds in Marcellus Shale flowback.

PubMed

Luek, Jenna L; Harir, Mourad; Schmitt-Kopplin, Philippe; Mouser, Paula J; Gonsior, Michael

2018-06-01

The chemistry of hydraulic fracturing fluids and wastewaters is complex and is known to vary by operator, geologic formation, and fluid age. A time series of hydraulic fracturing fluids, flowback fluids, and produced waters was collected from two adjacent Marcellus Shale gas wells for organic chemical composition analyses using ultrahigh resolution mass spectrometry. Hierarchical clustering was used to compare and extract ions related to different fluid ages and many halogenated organic molecular ions were identified in flowback fluids and early produced waters based on exact mass. Iodinated organic compounds were the dominant halogen class in these clusters and were nearly undetectable in hydraulic fracturing fluid prior to injection. The iodinated ions increased in flowback and remained elevated after ten months of well production. We suggest that these trends are mainly driven by dissolved organic matter reacting with reactive halogen species formed abiotically through oxidizing chemical additives applied to the well and biotically via iodide-oxidizing bacteria. Understanding the implications of these identified halogenated organic compounds will require future investigation in to their structures and environmental fate. Copyright © 2018 Elsevier Ltd. All rights reserved.

In situ measurements and modeling of reactive trace gases in a small biomass burning plume

NASA Astrophysics Data System (ADS)

Müller, Markus; Anderson, Bruce E.; Beyersdorf, Andreas J.; Crawford, James H.; Diskin, Glenn S.; Eichler, Philipp; Fried, Alan; Keutsch, Frank N.; Mikoviny, Tomas; Thornhill, Kenneth L.; Walega, James G.; Weinheimer, Andrew J.; Yang, Melissa; Yokelson, Robert J.; Wisthaler, Armin

2016-03-01

An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin to derive emission factors and followed ˜ 13.6 km downwind to observe chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatiotemporal resolution (10 m spatial/0.1 s temporal). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3, and 16 NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butanedione, and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV-1. Formaldehyde, acetaldehyde, 2-furfural, and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 pptV ppmV-1 CO. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a nearly explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into peroxyacetyl nitrate (PAN) and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45 ± 1.07 × 106 cm-3 in the

In situ measurements and modeling of reactive trace gases in a small biomass burning plume

NASA Astrophysics Data System (ADS)

Müller, M.; Anderson, B.; Beyersdorf, A.; Crawford, J. H.; Diskin, G.; Eichler, P.; Fried, A.; Keutsch, F. N.; Mikoviny, T.; Thornhill, K. L.; Walega, J. G.; Weinheimer, A. J.; Yang, M.; Yokelson, R.; Wisthaler, A.

2015-11-01

An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin for deriving emission factors and followed ~ 13.6 km downwind for observing chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatio-temporal resolution (10 m/0.1 s). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3 and 16 NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butandione and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV-1. Formaldehyde, acetaldehyde, 2-furfural and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 ppbV ppmV-1 CO emitted. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a near-explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into PAN and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45 ± 1.07 × 106 cm-3 in the plume. Formaldehyde, acetone

Cross-reactivity of Halogenated Platinum Salts

EPA Science Inventory

Halogenated platinum (Pt) salts are well-known respiratory sensitizers associated with the development of asthma. People may be exposed to a variety of platinum compounds in different contexts (e.g. occupationally, automobile exhaust). Published reports suggest that sensitizati...

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, John M.; Napier, John M.; Travaglini, Michael A.

1983-01-01

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

Loss of halogens from crystallized and glassy silicic volcanic rocks

USGS Publications Warehouse

Noble, D.C.; Smith, V.C.; Peck, L.C.

1967-01-01

One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

Do Halogen–Hydrogen Bond Donor Interactions Dominate the Favorable Contribution of Halogens to Ligand–Protein Binding?

PubMed Central

2017-01-01

Halogens are present in a significant number of drugs, contributing favorably to ligand–protein binding. Currently, the contribution of halogens, most notably chlorine and bromine, is largely attributed to halogen bonds involving favorable interactions with hydrogen bond acceptors. However, we show that halogens acting as hydrogen bond acceptors potentially make a more favorable contribution to ligand binding than halogen bonds based on quantum mechanical calculations. In addition, bioinformatics analysis of ligand–protein crystal structures shows the presence of significant numbers of such interactions. It is shown that interactions between halogens and hydrogen bond donors (HBDs) are dominated by perpendicular C–X···HBD orientations. Notably, the orientation dependence of the halogen–HBD (X–HBD) interactions is minimal over greater than 100° with favorable interaction energies ranging from −2 to −14 kcal/mol. This contrasts halogen bonds in that X–HBD interactions are substantially more favorable, being comparable to canonical hydrogen bonds, with a smaller orientation dependence, such that they make significant, favorable contributions to ligand–protein binding and, therefore, should be actively considered during rational ligand design. PMID:28657759

Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

PubMed

Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

2018-03-01

The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

Gas chromatographic analysis of trace impurities in chlorine trifluoride.

PubMed

Laurens, J B; Swinley, J M; de Coning, J P

2000-03-24

The gas chromatographic determination of trace gaseous impurities in highly reactive fluorinated gaseous matrices presents unique requirements to both equipment and techniques. Especially problematic are the gases normally present in ambient air namely oxygen and nitrogen. Analysing these gases at the low microl/l (ppm) level requires special equipment and this publication describes a custom-designed system utilising backflush column switching to protect the columns and detectors. A thermal conductivity detector with nickel filaments was used to determine ppm levels of impurities in ClF3.

Evaluating the potential for halogen bonding in ketosteroid isomerase’s oxyanion hole using unnatural amino acid mutagenesis

PubMed Central

Kraut, Daniel A; Churchil, Michael J; Dawson, Phillip E

2009-01-01

There has recently been an increasing interest in controlling macromolecular conformations and interactions through halogen bonding. Halogen bonds are favorable electrostatic interactions between polarized, electropositive chlorine, bromine or iodine atoms and electronegative atoms such as oxygen or nitrogen. These interactions have been likened to hydrogen bonds both in terms of their favored acceptor molecules, their geometries, and their energetics. We asked whether a halogen bond could replace a hydrogen bond in the oxyanion hole of ketosteroid isomerase, using semi-synthetic enzyme containing para-halogenated phenylalanine derivatives to replace the tyrosine hydrogen bond donor. Formation of a halogen bond to the oxyanion in the transition state would be expected to rescue the effects of mutation to phenylalanine, but all of the halogenated enzymes were comparable in activity to the phenylalanine mutant. We conclude that, at least in this active site, a halogen bond cannot functionally replace a hydrogen bond. PMID:19260691

Subtask 4.24 - Field Evaluation of Novel Approach for Obtaining Metal Emission Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pavlish, John; Laudal, Dennis; Thompson, Jeffrey

2013-12-31

Over the past two decades, emissions of mercury, nonmercury metals, and acid gases from energy generation and chemical production have increasingly become an environmental concern. On February 16, 2012, the U.S. Environmental Protection Agency (EPA) promulgated the Mercury and Air Toxics Standards (MATS) to reduce mercury, nonmercury metals, and HCl emissions from coal-fired power plants. The current reference methods for trace metals and halogens are wet-chemistry methods, EPA Method (M) 29 and M26A, respectively. As a possible alternative to EPA M29 and M26A, the Energy & Environmental Research Center (EERC) has developed a novel multielement sorbent trap (ME-ST) method tomore » be used to sample for trace elements and/or halogens. Testing was conducted at three different power plants, and the results show that for halogens, the ME-ST halogen (ME-ST-H) method did not show any significant bias compared to EPA M26A and appears to be a potential candidate to serve as an alternative to the reference method. For metals, the ME-ST metals (ME-ST-M) method offers a lower detection limit compared to EPA M29 and generally produced comparable data for Sb, As, Be, Cd, Co, Hg, and Se. Both the ME-ST-M and M29 had problems associated with high blanks for Ni, Pb, Cr, and Mn. Although this problem has been greatly reduced through improved trap design and material selection, additional research is still needed to explore possible longer sampling durations and/or selection of lower background materials before the ME-ST-M can be considered as a potential alternative method for all the trace metals listed in MATS.« less

Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride

NASA Astrophysics Data System (ADS)

Kononevich, Yuriy N.; Surin, Nikolay M.; Sazhnikov, Viacheslav A.; Svidchenko, Evgeniya A.; Aristarkhov, Vladimir M.; Safonov, Andrei A.; Bagaturyants, Alexander A.; Alfimov, Mikhail V.; Muzafarov, Aziz M.

2017-03-01

A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2-10 nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem = 433 and 445 nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction.

Studies of Trace Gas Chemical Cycles Using Inverse Methods and Global Chemical Transport Models

NASA Technical Reports Server (NTRS)

Prinn, Ronald G.

2003-01-01

We report progress in the first year, and summarize proposed work for the second year of the three-year dynamical-chemical modeling project devoted to: (a) development, testing, and refining of inverse methods for determining regional and global transient source and sink strengths for long lived gases important in ozone depletion and climate forcing, (b) utilization of inverse methods to determine these source/sink strengths using either MATCH (Model for Atmospheric Transport and Chemistry) which is based on analyzed observed wind fields or back-trajectories computed from these wind fields, (c) determination of global (and perhaps regional) average hydroxyl radical concentrations using inverse methods with multiple titrating gases, and (d) computation of the lifetimes and spatially resolved destruction rates of trace gases using 3D models. Important goals include determination of regional source strengths of methane, nitrous oxide, methyl bromide, and other climatically and chemically important biogenic/anthropogenic trace gases and also of halocarbons restricted by the Montreal protocol and its follow-on agreements and hydrohalocarbons now used as alternatives to the restricted halocarbons.

A Review of Hydrogen/Halogen Flow Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Kyu Taek; Tucker, Michael C.; Weber, Adam Z.

Flow batteries provide an energy-storage solution for various grid-related stability and service issues that arise as renewable-energy-generation technologies are adopted. Among the most promising flow-battery systems are those using hydrogen/halogen redox couples, which promise the possibility of meeting the cost target of the US Department of Energy (DOE), due to their fast and reversible kinetics and low materials cost. However, significant critical issues and barriers for their adoption remain. In this review of halogen/hydrogen systems, technical and performance issues, and research and development progress are reviewed. The information in this review can be used as a technical guide for researchmore » and development of related redox-flow-battery systems and other electrochemical technologies.« less

Method and apparatus for detecting halogenated hydrocarbons

DOEpatents

Monagle, Matthew; Coogan, John J.

1997-01-01

A halogenated hydrocarbon (HHC) detector is formed from a silent discharge (also called a dielectric barrier discharge) plasma generator. A silent discharge plasma device receives a gas sample that may contain one or more HHCs and produces free radicals and excited electrons for oxidizing the HHCs in the gas sample to produce water, carbon dioxide, and an acid including halogens in the HHCs. A detector is used to sensitively detect the presence of the acid. A conductivity cell detector combines the oxidation products with a solvent where dissociation of the acid increases the conductivity of the solvent. The conductivity cell output signal is then functionally related to the presence of HHCs in the gas sample. Other detectors include electrochemical cells, infrared spectrometers, and negative ion mobility spectrometers.

A Review of Hydrogen/Halogen Flow Cells

DOE PAGES

Cho, Kyu Taek; Tucker, Michael C.; Weber, Adam Z.

2016-05-17

Flow batteries provide an energy-storage solution for various grid-related stability and service issues that arise as renewable-energy-generation technologies are adopted. Among the most promising flow-battery systems are those using hydrogen/halogen redox couples, which promise the possibility of meeting the cost target of the US Department of Energy (DOE), due to their fast and reversible kinetics and low materials cost. However, significant critical issues and barriers for their adoption remain. In this review of halogen/hydrogen systems, technical and performance issues, and research and development progress are reviewed. The information in this review can be used as a technical guide for researchmore » and development of related redox-flow-battery systems and other electrochemical technologies.« less

WAVELENGTH-RESOLVED REMPI MASS SPECTROMETRY FOR THE MONITORING OF TOXIC INCINERATION TRACE GASES

EPA Science Inventory

Structure-selective measurement techniques are needed for the assessment of the toxic loading of incinerator gases. This review article shows that wavelength-resolved, resonance-enhanced, multiphoton- ionization (REMPY) mass spectrometry can be used to this end. In this case, how...

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies.

PubMed

Cerreia Vioglio, P; Szell, P M J; Chierotti, M R; Gobetto, R; Bryce, D L

2018-05-28

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81 Br covalently bonded to carbon remains impractical due to extremely large spectral widths, even at ultra-high magnetic fields. In contrast, nuclear quadrupole resonance (NQR) offers comparatively sharp resonances. Here, we demonstrate the abilities of 79/81 Br NQR to characterize the electronic changes in the C-Br···N halogen bonding motifs found in supramolecular assemblies constructed from 1,4-dibromotetrafluorobenzene and nitrogen-containing heterocycles. An increase in the bromine quadrupolar coupling constant is observed, which correlates linearly with the halogen bond distance ( d Br···N ). Notably, 79/81 Br NQR is able to distinguish between two symmetry-independent halogen bonds in the same crystal structure. This approach offers a rapid and reliable indication for the occurrence of a halogen bond, with experimental times limited only by the observation of 79/81 Br NQR resonances.

Modulation of the fibrillogenesis inhibition properties of two transthyretin ligands by halogenation.

PubMed

Cotrina, Ellen Y; Pinto, Marta; Bosch, Lluís; Vilà, Marta; Blasi, Daniel; Quintana, Jordi; Centeno, Nuria B; Arsequell, Gemma; Planas, Antoni; Valencia, Gregorio

2013-11-27

The amyloidogenic protein transthyretin (TTR) is thought to aggregate into amyloid fibrils by tetramer dissociation which can be inhibited by a number of small molecule compounds. Our analysis of a series of crystallographic protein-inhibitor complexes has shown no clear correlation between the observed molecular interactions and the in vitro activity of the inhibitors. From this analysis, it emerged that halogen bonding (XB) could be mediating some key interactions. Analysis of the halogenated derivatives of two well-known TTR inhibitors has shown that while flufenamic acid affinity for TTR was unchanged by halogenation, diflunisal gradually improves binding up to 1 order of magnitude after iodination through interactions that can be interpreted as a suboptimal XB (carbonyl Thr106: I...O distance 3.96-4.05 Å; C-I...O angle 152-156°) or as rather optimized van der Waals contacts or as a mixture of both. These results illustrate the potential of halogenation strategies in designing and optimizing TTR fibrillogenesis inhibitors.

Partial separation of halogens during the subduction of oceanic crust

NASA Astrophysics Data System (ADS)

Joachim, Bastian; Pawley, Alison; Lyon, Ian; Henkel, Torsten; Clay, Patricia L.; Ruzié, Lorraine; Burgess, Ray; Ballentine, Christopher J.

2014-05-01

Incompatible elements, such as halogens, have the potential to act as key tracers for volatile transport processes in Earth and planetary systems. The determination of halogen abundances and ratios in different mantle reservoirs gives us the ability to better understand volatile input mechanisms into the Earth's mantle through subduction of oceanic crust. Halogen partition coefficients were experimentally determined between forsterite, orthopyroxene and silicate melt at pressures ranging from 1.0 to 2.3 GPa and temperatures ranging from 1500-1600°C, thus representing partial melting conditions of the Earth's mantle. Combining our data with results of recent studies (Beyer et al. 2012; Dalou et al. 2012) shows that halogen partitioning between forsterite and melt increases by factors of about 1000 (fluorine) and 100 (chlorine) between 1300°C and 1600°C and does not show any pressure dependence. Chlorine partitioning between orthopyroxene and melt increases by a factor of about 1500 for a temperature increase of 100°C (anywhere between 1300°C and 1600°C), but decreases by a factor of about 1500 for a pressure increase of 1.0 GPa (anywhere between 1.0 GPa and 2.5 GPa). At similar P-T conditions, a comparable effect is observed for the fluorine partitioning behaviour, which increases by 500-fold for a temperature increase of 100°C and decreases with increasing pressure. Halogen abundances in mid-ocean ridge basalts (MORB; F=3-15, Cl=0.5-14ppm) and ocean island basalts (OIB; F=35-65, Cl=21-55 ppm) source regions were estimated by combining our experimentally determined partition coefficients with natural halogen concentrations in oceanic basalts (e.g. Ruzié et al. 2012). The estimated chlorine OIB source mantle concentration is in almost perfect agreement with primitive mantle estimates (Palme and O'Neill 2003). If we expect an OIB source mantle slightly depleted in incompatible elements, this suggests that at least small amounts of chlorine are recycled deep

Management of exposure to waste anesthetic gases.

PubMed

Smith, Francis Duval

2010-04-01

Anesthetic agents were developed in the 1700s, and nitrous oxide was first used in 1884. Research on the effects of waste anesthetic gas exposure started appearing in the literature in 1967. Short-term exposure causes lethargy and fatigue, and long-term exposure may be linked to spontaneous abortion, congenital abnormalities, infertility, premature births, cancer, and renal and hepatic disease. Today, perioperative staff members are exposed to trace amounts of waste anesthetic gas, and although this exposure cannot be eliminated, it can be controlled. Health care facilities are required to develop, implement, measure, and control practices to reduce anesthetic gas exposure to the lowest practical level. Exposure levels must be measured every six months and maintained at less than 25 parts per million for nitrous oxide and 2 parts per million for halogenated agents to be compliant with Occupational Safety and Health Administration standards. Copyright 2010 AORN, Inc. Published by Elsevier Inc. All rights reserved.

Martian fluid and Martian weathering signatures identified in Nakhla, NWA 998 and MIL 03346 by halogen and noble gas analysis

NASA Astrophysics Data System (ADS)

Cartwright, J. A.; Gilmour, J. D.; Burgess, R.

2013-03-01

We report argon (Ar) noble gas, Ar-Ar ages and halogen abundances (Cl, Br, I) of Martian nakhlites Nakhla, NWA 998 and MIL 03346 to determine the presence of Martian hydrous fluids and weathering products. Neutron-irradiated samples were either crushed and step-heated (Nakhla only), or simply step-heated using a laser or furnace, and analysed for noble gases using an extension of the 40Ar-39Ar technique to determine halogen abundances. The data obtained provide the first isotopic evidence for a trapped fluid that is Cl-rich, has a strong correlation with 40ArXS (40ArXS = 40Armeasured - 40Arradiogenic) and displays 40ArXS/36Ar of ˜1000 - consistent with the Martian atmosphere. This component was released predominantly in the low temperature and crush experiments, which may suggest a fluid inclusion host. For the halogens, we observe similar Br/Cl and I/Cl ratios between the nakhlites and terrestrial reservoirs, which is surprising given the absence of crustal recycling, organic matter and frequent fluid activity on Mars. In particular, Br/Cl ratios in our Nakhla samples (especially olivine) are consistent with previously analysed Martian weathering products, and both low temperature and crush analyses show a similar trend to the evaporation of seawater. This may indicate that surface brines play an important role on Mars and on halogen assemblages within Martian meteorites and rocks. Elevated I/Cl ratios in the low temperature NWA 998 and MIL 03346 releases may relate to in situ terrestrial contamination, though we are unable to distinguish between low temperature terrestrial or Martian components. Whilst estimates of the amount of water present based on the 36Ar concentrations are too high to be explained by a fluid component alone, they are consistent with a mixed-phase inclusion (gas and fluid) or with shock-implanted Martian atmospheric argon. The observed fluid is dilute (low salinity, but high Br/Cl and I/Cl ratios), contains a Martian atmospheric component

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wang, Shuxiao; Wu, Qingru; Wang, Fengyang; Lin, Che-Jen; Zhang, Leiming; Hui, Mulin; Yang, Mei; Su, Haitao; Hao, Jiming

2016-02-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, L.; Wang, S. X.; Wu, Q. R.; Wang, F. Y.; Lin, C.-J.; Zhang, L. M.; Hui, M. L.; Hao, J. M.

2015-11-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, municipal solid waste incinerators, and biomass burning. Mercury in coal, ores and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of gaseous elemental mercury (Hg0) to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g.,TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non

Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products.

PubMed

Odabasi, Mustafa

2008-03-01

Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and

Twenty Five Years of Airborne Observations of Ozone-Depleting and Climate-Related Gases in the Upper Troposphere and Lower Stratosphere.

NASA Astrophysics Data System (ADS)

Elkins, J. W.; Moore, F. L.; Hintsa, E. J.; Dutton, G. S.; Nance, J. D.; Hall, B. D.

2016-12-01

NOAA scientists started in situ airborne measurements of two strong ozone-depleting gases or chlorofluorocarbons, CFC-11 and CFC-113 in 1991 on the NASA ER-2 aircraft with a two-channel gas chromatograph, Airborne Chromatograph for Atmospheric Trace Species (ACATS). We broaden our list of gases to include more ozone-depleting and other climate-related gases. An improved 4-channel gas chromatograph that included N2O, SF6, CFC-11, -12, -113, halon-1211, CCl4, CH3CCl3, CH4, CO, and H2 was added to the ER-2 aircraft in 1994. As CFC replacements took hold, we add a gas chromatograph-mass spectrometer system, PAN and other Trace Hydro-halocarbon Experiment (PANTHER), to examine shorter-lived gases mainly in the upper troposphere. These airborne measurements were to complement of ground-based flask and in situ measurements from the NOAA Halocarbon and other Trace Species Network. This talk will show results from a tropical study, Airborne Tropical Tropopause Experiment (ATTREX) on the NASA Global Hawk aircraft and preliminary results from the Atmospheric Tomography Mission (ATom) conducted in August 2016 on the NASA DC-8 aircraft. A detrended, gridded, latitudinal distribution of SF6 is shown in the figure below for the years of 1994 through 2014. Such a plot may be useful to atmospheric modelers trying to capture transport or calculate emissions.

The Role of Halogens in High-Grade Metamorphism and Anatexis

NASA Astrophysics Data System (ADS)

Aranovich, L.; Safonov, O.

2016-12-01

We review factors controlling the distribution of the two major halogens, F and Cl, in high-grade metamorphic rocks; their compositional correlations and partitioning between minerals; experimental data on stability and phase equilibria of the halogen-bearing minerals; the influence of halogens on Fe-Mg exchange reactions; and the means of estimating concentrations/activity of halogen species concentration/ activity in the fluid phase ("chlorimetry and fluorimetry") via calculation of equilibrium conditions for mineral assemblages containing halogen-bearing phases. Clear negative correlation between the F content and XFe=Fe/(Fe+Mg) suggests that natural biotite and amphibole obey the Fe-F avoidance rule. A strong positive correlation exists between K and Cl in amphibole. A scattering of points on the XFe -Cl and TiO2- Cl diagrams indicate the possible involvement of an exotic Cl-rich phase (fluid or melt) during the formation of Cl-bearing biotite and amphibole. Fluorine and Cl substituting for OH-groups substantially stabilize minerals relative to dehydration and melting. They should also strongly affect partitioning of Fe and Mg between biotite, amphibole and anhydrous minerals. This effect is quantified for Fe-Mg exchange reactions involving biotite (Zhu and Sverjensky, 1992), but remains to be evaluated for amphibole. Calculations based on recent thermodynamic systematics show that the relatively Mg-rich, Cl-poor biotite (for example, XFe = 0.4 and about 0.2 wt.% Cl) may coexist with a fairly Cl-rich fluid, i.e. total Cl/(Cl+H2O) from 0.1-0.3, depending on the assemblage, under granulite facies P-T conditions. Alkali (and Ca) metasomatism caused by interaction of high grade rocks with halogen-bearing fluids has major impact on the subsolidus phase transformations and melting processes during high-grade metamorphism and anatexis. For example, an increase in sodium content in plagioclase (Pl) by 20 mol% due to infiltration of Na- fluid into the quartz (Qtz

Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

NASA Astrophysics Data System (ADS)

Sumner, A. J.; Plata, D.

2017-12-01

Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

40 CFR 721.8675 - Halogenated pyridines.

Code of Federal Regulations, 2013 CFR

2013-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8675 Halogenated pyridines. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

40 CFR 721.8675 - Halogenated pyridines.

Code of Federal Regulations, 2014 CFR

2014-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8675 Halogenated pyridines. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

40 CFR 721.8675 - Halogenated pyridines.

Code of Federal Regulations, 2012 CFR

2012-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8675 Halogenated pyridines. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

Inorganic Halogen Oxidizer Research

DTIC Science & Technology

1975-02-26

K. 0. Christe and C. J. Schack, Advances Inorg. Chem. Radiochem. 15. "The NF * Radical Cation. Esr Studies of Radiation Effects in NF„+ Salts...and 25°) in a wide variety of polar and nonpolar solvents, such as aqueous solutions, alcohols, ketones , esters, ethers , and aromatic and halogenated... Studies of Radiation Effects in NF, Salts = 4 S. P. Mishra, M. C R. Symons, K. 0. Christe, R. D. Wilson and R. I. Wagner Received. . . August .9

Photoacoustic Techniques for Trace Gas Sensing Based on Semiconductor Laser Sources

PubMed Central

Elia, Angela; Lugarà, Pietro Mario; Di Franco, Cinzia; Spagnolo, Vincenzo

2009-01-01

The paper provides an overview on the use of photoacoustic sensors based on semiconductor laser sources for the detection of trace gases. We review the results obtained using standard, differential and quartz enhanced photoacoustic techniques. PMID:22303143

Trace Gas Trends in the Stratosphere: 1991-2005

NASA Astrophysics Data System (ADS)

Elkins, J. W.; Moore, F. L.; Dutton, G. S.; Hurst, D. F.; Ray, E. A.; Montzka, S. A.; Butler, J. H.; Fahey, D. W.; Hall, B. H.; Atlas, E.; Wofsy, S. C.; Romashkin, P. A.

2005-05-01

The first NOAA airborne gas chromatograph measured chlorofluorocarbon-11 (CFC-11) and CFC-113 during the Arctic Airborne Stratospheric Experiment in 1991-1992. In 1994, we added nitrous oxide (N2O), sulfur hexafluoride (SF6), CFC-12, halon-1211, methyl chloroform, carbon tetrachloride, methane, and hydrogen. NOAA scientists have since operated five airborne gas chromatographs on NASA airborne platforms, including the NASA Jet Propulsion Laboratory (JPL) balloon gondola and ER-2, WB-57F, DC-8, and NASA Altair Unmanned Air Vehicle (UAV) aircraft. Using these in situ measurements and tracer-tracer correlations from flask observations for the unmeasured halogen species (HCFCs and methyl halides including methyl chloride and bromide), we have estimated trends of total chlorine and bromine in the stratosphere. The determination of inorganic equivalent chlorine (Cl + 45*Br) requires the trend of tropospheric equivalent chlorine and the mean age of the parcel of stratospheric air. In general, there is good agreement between the mean age of the air mass calculations using carbon dioxide and SF6, except for regions of extreme down welling of mesospheric air where SF6 is consumed. Tropospheric trends of the methyl halides have been compiled against stable standards. We operated a airborne gas chromatograph on the Sage 3 Ozone Loss Validation Experiment (SOLVE-II) mission from Kiruna, Sweden during 2002. It measured the major HCFCs and methyl halides, so that these compounds do not have to be estimated from tracer-tracer correlations in the future. In 2005, we have added a new lightweight airborne instrument (<25 kg) that can measure CFC-11, CFC-12, halon-1211, SF6, N2O, and ozone. This instrument can operate on small or UAV aircraft and will be used for Aura satellite validation. This presentation will show trends for selected trace gases and our estimates of total equivalent chlorine stratospheric trends since 1991.

Volatile Halogenated Organic Compounds Released to Seawater from Temperate Marine Macroalgae

NASA Astrophysics Data System (ADS)

Gschwend, Philip M.; Macfarlane, John K.; Newman, Kathleen A.

1985-03-01

Volatile halogenated organic compounds synthesized by various industrial processes are troublesome pollutants because they are persistent in terrestrial ecosystems and because they may be present in sufficient quantities to alter the natural atmospheric cycles of the halogens. Certain of these compounds, including polybromomethanes and several previously unobserved alkyl monohalides and dihalides, appear to be natural products of the marine environment. A variety of temperate marine macroalgae (the brown algae Ascophyllum nodosum and Fucus vesiculosis, the green algae Enteromorpha linza and Ulva lacta, and the red alga Gigartina stellata) not only contain volatile halogenated organic compounds but also release them to seawater at rates of nanograms to micrograms of each compound per gram of dry algae per day. The macroalgae may be an important source of bromine-containing material released to the atmosphere.

"Variations in trace metal and halogen ratios in magmatic gases through an eruptive. Cycle of the Pu'u O'o Vent, Kilauea, Hawaii: July-August 1985""

NASA Astrophysics Data System (ADS)

Miller, Theresa L.; Zoller, William H.; Crowe, Bruce M.; Finnegan, David L.

1990-08-01

Particle and gas samples were obtained before and after eruptive episode 35 in July and August 1985 at the fuming Pu'u O'o vent, Kilauea volcano, Hawaii. The sampling system employed consisted of a particle filter followed by four 7LiOH treated filters to collect acidic gases. The filters were analyzed using instrumental neutron activation analysis (INAA). The results indicate that Br/Cl and Re/Cl ratios do not fluctuate through an eruption cycle but the F/Cl, F/Br and metal/Cl ratios (In and Cd) do change through the cycle. An inverse relationship between F/Cl and metal/Cl was observed. The changes are probably due to influxes of relatively undegassed magma during the repose period releasing fume with lower F/Cl, F/Br and higher metal/Cl ratios. As the magma in the Pu'u O'o conduit gradually degasses either before or several days after an eruptive episode, F/Cl and F/Br ratios increase and the metal/Cl ratios decrease. One sample collected on July 24, two days before eruptive episode 35, did not follow this general trend. This can be explained by a gas pulse from a deeper, less degassed portion of magma making its way to the top of the conduit.

Halogen free benzoxazine based curable compositions for high T.sub.g applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tietze, Roger; Nguyen, Yen-Loan

A method for forming a halogen-free curable composition containing a benzoxazine monomer, at least one epoxy resin, a catalyst, a toughening agent and a solvent. The halogen-free curable composition is especially suited for use in automobile and aerospace applications since the composition, upon curing, produces a composite having a high glass transition temperature.

α-Halogenated oxaphosphinanes: Synthesis, unexpected reactions and evaluation as inhibitors of cancer cell proliferation.

PubMed

Babouri, Rachida; Rolland, Marc; Sainte-Catherine, Odile; Kabouche, Zahia; Lecouvey, Marc; Bakalara, Norbert; Volle, Jean-Noël; Virieux, David; Pirat, Jean-Luc

2015-11-02

This paper describes the preparation and the biological evaluation of α-halogenated oxaphosphinanes. These halogen derivatives were synthetized from a short and stereoselective synthetic sequence starting by previously described hydroxy-precursors 1 and 2 with respectively a glucose and mannose-like configuration. The in vitro biological tests of these unnatural halogenated phosphinosugars, on several cell lines, highlighted, for some of them, their antiproliferative and anti migration and invasion properties at nanomolar concentration. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

DOEpatents

Miura, Michiko; Wu, Haitao

2013-05-21

The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

Structure-Energy Relationships of Halogen Bonds in Proteins.

PubMed

Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

2017-06-06

The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

Trace gas retrievals from Airborne Compact Atmospheric Mapper (ACAM) observations during the 2011 DISCOVER-AQ flight campaign

NASA Astrophysics Data System (ADS)

Liu, X.; Kowalewski, M. G.; Janz, S. J.; Bhartia, P. K.; Chance, K.; Krotkov, N. A.; Pickering, K. E.; Crawford, J. H.

2011-12-01

The DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) mission has just finished its first flight campaign in the Baltimore-Washington D.C. area in July 2011. The ACAM, flown on board the NASA UC-12 aircraft, includes two spectrographs covering the spectral region 304-900 nm and a high-definition video camera, and is expected to provide column measurements of several important air quality trace gases and aerosols for the DISCOVER-AQ mission. The quick look results for NO2 have been shown to very useful in capturing the strong spatiotemporal variability of NO2. Preliminary fitting of UV/Visible spectra has shown that ACAM measurements have adequate signal to noise ratio to measure the trace gases O2, NO2, HCHO, and maybe SO2 and CHOCHO, at individual pixel resolution, although a great deal of effort is needed to improve the instrument calibration and derive proper reference spectrum for retrieving absolute trace gas column densities. In this study, we present analysis of ACAM instrument calibration including slit function, wavelength registration, and radiometric calibration for both nadir-viewing and zenith-sky measurements. Based on this analysis, an irradiance reference spectrum at ACAM resolution will be derived from a high-resolution reference spectrum with additional correction to account for instrument calibration. Using the derived reference spectrum and/or the measured zenith sky measurements, we will perform non-linear least squares fitting to investigate the retrievals of slant column densities of these trace gases from ACAM measurements, and also use an optimal estimation based algorithm including full radiative transfer calculations to derive the vertical column densities of these trace gases. The initial results will be compared with available in-situ and ground-based measurements taken during the DISCOVER-AQ campaign.

Formation of halogen-induced secondary organic aerosol (XOA)

NASA Astrophysics Data System (ADS)

Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

2013-04-01

Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

TRACE GAS CONCENTRATIONS IN SMALL STREAMS OF THE GEORGIA PIEDMONT

EPA Science Inventory

Seventeen headwater watersheds within the SFBR watershed ranging from 0.5 to 3.4 km2 were selected. We have been monitoring concentrations of the trace gases nitrous oxide, methane, and carbon dioxide, and other parameters (T, conductivity, dissolved oxygen, pH, nutrients, flow r...

Scavenging of radioactive soluble gases from inhomogeneous atmosphere by evaporating rain droplets.

PubMed

Elperin, Tov; Fominykh, Andrew; Krasovitov, Boris

2015-05-01

We analyze effects of inhomogeneous concentration and temperature distributions in the atmosphere, rain droplet evaporation and radioactive decay of soluble gases on the rate of trace gas scavenging by rain. We employ a one-dimensional model of precipitation scavenging of radioactive soluble gaseous pollutants that is valid for small gradients and non-uniform initial altitudinal distributions of temperature and concentration in the atmosphere. We assume that conditions of equilibrium evaporation of rain droplets are fulfilled. It is demonstrated that transient altitudinal distribution of concentration under the influence of rain is determined by the linear wave equation that describes propagation of a scavenging wave front. The obtained equation is solved by the method of characteristics. Scavenging coefficients are calculated for wet removal of gaseous iodine-131 and tritiated water vapor (HTO) for the exponential initial distribution of trace gases concentration in the atmosphere and linear temperature distribution. Theoretical predictions of the dependence of the magnitude of the scavenging coefficient on rain intensity for tritiated water vapor are in good agreement with the available atmospheric measurements. Copyright © 2015 Elsevier Ltd. All rights reserved.

Skin Sensitizing Potency of Halogenated Platinum Salts.

EPA Science Inventory

The relationship between occupational exposure to halogenated platinum (Pt) salts and Pt-specific allergic sensitization is well-established. Although human case reports and clinical studies demonstrate that Pt salts are potent skin sensitizers, no studies have been published tha...

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

PubMed

Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

2015-08-04

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

PubMed

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

PubMed

Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

2016-09-01

Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

DESTRUCTION OF HALOGENATED HYDROCARBONS WITH SOLVATED ELECTRONS IN THE PRESENCE OF WATER. (R826180)

EPA Science Inventory

Model halogenated aromatic and aliphatic hydrocarbons and halogenated phenols were dehalogenated in seconds by solvated electrons generated from sodium in both anhydrous liquid ammonia and ammonia/water solutions. The minimum sodium required to completely dehalogenate these mo...

Seasonal and spatial changes in trace gases over megacities from Aura TES observations: two case studies

NASA Astrophysics Data System (ADS)

Cady-Pereira, Karen E.; Payne, Vivienne H.; Neu, Jessica L.; Bowman, Kevin W.; Miyazaki, Kazuyuki; Marais, Eloise A.; Kulawik, Susan; Tzompa-Sosa, Zitely A.; Hegarty, Jennifer D.

2017-08-01

The Aura Tropospheric Emission Spectrometer (TES) is collecting closely spaced observations over 19 megacities. The objective is to obtain measurements that will lead to better understanding of the processes affecting air quality in and around these cities, and to better estimates of the seasonal and interannual variability. We explore the TES measurements of ozone, ammonia, methanol and formic acid collected around the Mexico City metropolitan area (MCMA) and in the vicinity of Lagos (Nigeria). The TES data exhibit seasonal signals that are correlated with Atmospheric Infrared Sounder (AIRS) CO and Moderate Resolution Imaging Spectroradiometer (MODIS) aerosol optical depth (AOD), with in situ measurements in the MCMA and with Goddard Earth Observing System (GEOS)-Chem model output in the Lagos area. TES was able to detect an extreme pollution event in the MCMA on 9 April 2013, which is also evident in the in situ data. TES data also show that biomass burning has a greater impact south of the city than in the caldera where Mexico City is located. TES measured enhanced values of the four species over the Gulf of Guinea south of Lagos. Since it observes many cities from the same platform with the same instrument and applies the same retrieval algorithms, TES data provide a very useful tool for easily comparing air quality measures of two or more cities. We compare the data from the MCMA and Lagos, and show that, while the MCMA has occasional extreme pollution events, Lagos consistently has higher levels of these trace gases.

Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective

PubMed Central

Wolters, Lando P; Bickelhaupt, F Matthias

2012-01-01

We have carried out extensive computational analyses of the structure and bonding mechanism in trihalides DX⋅⋅⋅A− and the analogous hydrogen-bonded complexes DH⋅⋅⋅A− (D, X, A=F, Cl, Br, I) using relativistic density functional theory (DFT) at zeroth-order regular approximation ZORA-BP86/TZ2P. One purpose was to obtain a set of consistent data from which reliable trends in structure and stability can be inferred over a large range of systems. The main objective was to achieve a detailed understanding of the nature of halogen bonds, how they resemble, and also how they differ from, the better understood hydrogen bonds. Thus, we present an accurate physical model of the halogen bond based on quantitative Kohn–Sham molecular orbital (MO) theory, energy decomposition analyses (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. It appears that the halogen bond in DX⋅⋅⋅A− arises not only from classical electrostatic attraction but also receives substantial stabilization from HOMO–LUMO interactions between the lone pair of A− and the σ* orbital of D–X. PMID:24551497

Variations in trace metal and halogen ratios in magmatic gases through an eruptive cycle of the Pu'u O'o vent, Kilauea, Hawaii: July-August 1985

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, T.L.; Zoller, W.H.; Crowe, B.M.

1990-08-10

Particle and gas samples were obtained before and after eruptive episode 35 in July and August 1985 at the fuming Pu'u O'o vent, Kilauea volcano, Hawaii. The sampling system employed consisted of a particle filter followed by four {sup 7}LiOH treated filters to collect acidic gases. The filters were analyzed using instrumental neutron activation analysis (INAA). The results indicate that Br/Cl and Re/Cl ratios do not fluctuate through an eruption cycle but the F/Cl, F/Br and metal/Cl ratios (In and Cd) do change through the cycle. An inverse relationship between F/Cl and metal/Cl was observed. The changes are probably duemore » to influxes of relatively undegassed magma during the repose period releasing fume with lower F/Cl, F/BR and higher metal/Cl ratios. As the magma in the Pu'u O'o conduit gradually degasses either before or several days after an eruptive episode, F/Cl and F/Br ratios increase and the metal/Cl ratios decrease. One sample collected on July 24, two days before eruptive episode 35, did not follow this general trend. This can be explained by a gas pulse from a deeper, less degassed portion of magma making its way to the top of the conduit.« less

40 CFR 721.535 - Halogenated alkane (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... Section 721.535 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to...

Chemical Action of Halogenated Agents in Fire Extinguishing

NASA Technical Reports Server (NTRS)

Belles, Frank E.

1955-01-01

The action of halogenated agents in preventing flame propagation in fuel-air mixtures in laboratory tests is discussed in terms of a possible chemical mechanism. The mechanism chosen is that of chain-breaking reactions between agent and active particles (hydrogen and oxygen atoms and hydroxyl radicsls). Data from the literature on the flammability peaks of n-heptane agent-air mixtures are treated. Ratings of agent effectiveness in terms of the fuel equivalent of the agent, based on both fuel and agent concentrations at the peak, are proposed as preferable to ratings in terms of agent concentration alone. These fuel-equivalent ratings are roughly correlated by reactivities assigned to halogen and hydrogen atoms in the agent molecules. It is concluded that the presence of hydrogen in agent need not reduce its fire-fighting ability, provided there is enough halogen to make the agent nonflammable. A method is presented for estimating from quenching-distance data a rate constant for the reaction of agent with active particles. A quantitative result is obtained for methyl bromide. This rate constant predicts the observed peak concentration of methyl bromide quite well. However, more data are needed to prove the validity of the method. The assumption that hal.ogenatedagents act mainly by chain-bresking reactions with active particles is consistent with the experimental facts and should help guide the selection of agents for further tests.

Study of different operational modes of the IAP 2-port-DOAS instrument for atmospheric trace gases investigation during CINDI-2 campaign basing on residual noise analysis

NASA Astrophysics Data System (ADS)

Borovski, A.; Postylyakov, O.; Elokhov, A.; Bruchkovski, I.

2017-11-01

An instrument for measuring atmospheric trace gases by DOAS method using scattered solar radiation was developed in A.M.Obukhov IAP RAS. The instrument layout is based on the lab Shamrock 303i spectrograph supplemented by 2-port radiation input system employing optical fiber. Optical ports may be used with a telescope with fixed field of view or with a scanning MAX-DOAS unit. MAX-DOAS unit port will be used for investigation of gas contents and profiles in the low troposphere. In September 2016 the IAP instrument participated in the CINDI-2 campaign, held in the Netherlands. CINDI 2 (2nd Cabauw Intercomparison of Nitrogen Dioxide Measuring Instruments) involves about 40 instruments quasi-synchronously performing DOAS measurements of NO2 and other trace gases. During the campaign the instrument ports had telescopes A and B with similar field of view of about 0.3°. Telescope A was always directed to the zenith. Telescope B was directed at 5° elevation angle. Two gratings were installed in the spectrometer. They provide different spectral resolution (FWHM 0.4 and 0.8 nm respectively) and spectral window width ( 70 and 140 nm respectively). During CINDI-2 campaign we performed test measurements in UV and visible wavelength ranges to investigate instrument stability and retrieval errors of NO2 and HCHO contents. We perform the preliminary error analysis of retrieval of the NO2 and HCHO differential slant column densities using spectra measured in four modes of the instrument basing on residual noise analysis in this paper. It was found that rotation of grating turret does not significantly affected on quality of NO2 DSCD retrieval from spectra which measured in visible spectral region. Influence of grating turret rotation is much more significant for gas DSCD retrieval from spectra which measured in UV spectral region. Standard deviation of retrieval error points to presence of some systematic error.

Energetics of halogen impurities in thorium dioxide

NASA Astrophysics Data System (ADS)

Kuganathan, Navaratnarajah; Ghosh, Partha S.; Arya, Ashok K.; Dey, Gautam K.; Grimes, Robin W.

2017-11-01

Defect energies for halogen impurity atoms (Cl, Br and I) in thoria are calculated using the generalized gradient approximation and projector augmented plane wave potentials under the framework of density functional theory. The energy to place a halogen atom at a pre-existing lattice site is the incorporation energy. Seven sites are considered: octahedral interstitial, O vacancy, Th vacancy, Th-O di-vacancy cluster (DV) and the three O-Th-O tri-vacancy cluster (NTV) configurations. For point defects and vacancy clusters, neutral and all possible defect charge states up to full formal charge are considered. The most favourable incorporation site for Cl is the singly charged positive oxygen vacancy while for Br and I it is the NTV1 cluster. By considering the energy to form the defect sites, solution energies are generated. These show that in both ThO2-x and ThO2 the most favourable solution equilibrium site for halides is the single positively charged oxygen vacancy (although in ThO2, I demonstrates the same solubility in the NTV1 and DV clusters). Solution energies are much lower in ThO2-x than in ThO2 indicating that stoichiometry is a significant factor in determining solubility. In ThO2, all three halogens are highly insoluble and in ThO2-x Br and I remain insoluble. Although ½Cl2 is soluble in ThO2-x alternative phases such as ZrCl4 exist which are of lower energy.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

Sources of halogens in the environment, influences on human and animal health.

PubMed

Fuge, R

1988-06-01

Of the halogens, fluorine has the highest crustal abundance (544 mg/kg) while iodine has the lowest (0.25 mg/kg), however, chlorine is by far the most abundant halogen in the cosmos. The geochemistries of the four naturally occurring halogens have some similarities with fluorine, chlorine and bromine being classified as lithophile elements while iodine is more chalcophile in nature. Bromine and iodine behave in a similar fashion in the secondary environment and could be classified as biophile elements being concentrated in organic matter. Chlorine, bromine and iodine are strongly enriched in the sea while iodine and to a lesser extent bromine are further concentrated in the marine algae.Apart from the occurrence of fluorine in fluorite (CaF2) there are few commonly occurring minerals which contain the halogens as essential constituents. In the igneous environment fluorine and chlorine tend to occupy hydroxyl lattice sites in micas, amphiboles, apatites etc., while in sediments clays can contain appreciable quantities of these elements. Bromine and iodine, however, would be unlikely to fit into the lattice sites of common rock-forming minerals.Bromine, like iodine, is probably volatilised from the marine environment and is carried on to land surfaces. This behaviour of iodine and bromine is reflected in the increased I/CI and Br/CI ratios of surface run-off in continental compared with near coastal environments.Limited information on the soil geochemistry of the halogens suggests that the soil contents of chlorine, bromine and iodine are influenced by proximity to the sea. Soil fluorine, however, is generally dependent on its content in the parent material. In some areas pollutant sources of the halogens contribute appreciably to their concentration in the environment.Iodine and chlorine are essential elements for mammals and fluorine has been shown to have beneficial effects on bone and tooth formation. However, excess quantities of dietary fluorine can be harmful

Mouse Model of Halogenated Platinum Salt Hypersensitivity

EPA Science Inventory

Occupational exposure to halogenated platinum salts can trigger the development of asthma. Concern for increased asthma risk exists for the general population due to the use of platinum (Pt) in catalytic converters and its emerging use as a diesel fuel additive. To investigate a...

Technology for radiation efficiency measurement of high-power halogen tungsten lamp used in calibration of high-energy laser energy meter.

PubMed

Wei, Ji Feng; Hu, Xiao Yang; Sun, Li Qun; Zhang, Kai; Chang, Yan

2015-03-20

The calibration method using a high-power halogen tungsten lamp as a calibration source has many advantages such as strong equivalence and high power, so it is very fit for the calibration of high-energy laser energy meters. However, high-power halogen tungsten lamps after power-off still reserve much residual energy and continually radiate energy, which is difficult to be measured. Two measuring systems were found to solve the problems. One system is composed of an integrating sphere and two optical spectrometers, which can accurately characterize the radiative spectra and power-time variation of the halogen tungsten lamp. This measuring system was then calibrated using a normal halogen tungsten lamp made of the same material as the high-power halogen tungsten lamp. In this way, the radiation efficiency of the halogen tungsten lamp after power-off can be quantitatively measured. In the other measuring system, a wide-spectrum power meter was installed far away from the halogen tungsten lamp; thus, the lamp can be regarded as a point light source. The radiation efficiency of residual energy from the halogen tungsten lamp was computed on the basis of geometrical relations. The results show that the halogen tungsten lamp's radiation efficiency was improved with power-on time but did not change under constant power-on time/energy. All the tested halogen tungsten lamps reached 89.3% of radiation efficiency at 50 s after power-on. After power-off, the residual energy in the halogen tungsten lamp gradually dropped to less than 10% of the initial radiation power, and the radiation efficiency changed with time. The final total radiation energy was decided by the halogen tungsten lamp's radiation efficiency, the radiation efficiency of residual energy, and the total power consumption. The measuring uncertainty of total radiation energy was 2.4% (here, the confidence factor is two).

Inorganic Halogen Oxidizer Research

DTIC Science & Technology

1981-04-21

International Rocketdyne Division 6633 Canoga Avenue Canoga Park, California 91304 RI/R.D8l1-14O A ’N-NUAL REPORT INORGANIC HALOGEN OXIDIZER RESEARCH (I...March 1980 through 8 February 198L) 21 April 1981 "Contract N00014-79-C-0176 . GO. 95067 . , Office of Naval Research I-- Power Branch , ,, Code 473...Office of Naval Research Power Branch 11 I-ar Ccovie 473 ~ UMBER OF PA’E1 Arlington. VA 22217 . 76" 74 AONIYONING AGENCY NAME III Dw~S~ d, I f,. .f

Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

NASA Astrophysics Data System (ADS)

Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

2014-12-01

Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

Nighttime chemical evolution of aerosol and trace gases in a power plant plume: Implications for secondary organic nitrate and organosulfate aerosol formation, NO₃ radical chemistry, and N₂O₅ heterogeneous hydrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaveri, Rahul A.; Berkowitz, Carl M.; Brechtel, Fred J.

Chemical evolution of aerosols and trace gases in the Salem Harbor power plant plume was monitored with the DOE G-1 aircraft on the night of July 30-31, 2002. Quasi-Lagrangian sampling in the plume at increasing downwind distances/processing times was guided by a constant-volume tetroon that was released near the power plant at sunset. While no evidence of fly ash particles was found, concentrations of particulate organics, sulfate, and nitrate were higher in the plume than in the nearby background air. These species were internally mixed and the particles were acidic, suggesting that particulate nitrate was in the form of organicmore » nitrate. The enhanced particulate organic and nitrate masses in the plume were inferred to be as secondary organic aerosol, possibly formed from the NO3 radical-initiated oxidation of isoprene and other trace organic gases in the presence of acidic sulfate particles. The enhanced particulate sulfate concentrations observed in the plume were attributed to direct emissions of gaseous SO3/H2SO4 from the power plant. Furthermore, concentration of nucleation mode particles was significantly higher in the plume than in background air, suggesting that some of the emitted H2SO4 had nucleated to form new particles. Spectromicroscopic analyses of particle samples suggested that some sulfate was likely in the form of organosulfates. Constrained Lagrangian model analysis of the aircraft and tetroon observations showed that heterogeneous hydrolysis of N2O5 was negligibly slow. These results have significant implications for several scientific and regulatory issues related to the impacts of power plant emissions on atmospheric chemistry, air quality, visibility, and climate.« less

Halogens and the Chemistry of the Free Troposphere

NASA Technical Reports Server (NTRS)

Lary, David John

2004-01-01

The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of BrONO2 alone can contribute more than 35% of the HNO3 production rate in the free-troposphere.

Auger analysis of films formed on metals in sliding contact with halogenated polymers

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1974-01-01

The use of Auger electron spectroscopy (AES) to search for transferred polymer must contend with the fact that there has been no published work on Auger analysis of polymers. Since this is a new area for AES, the Auger spectra of polymers and of halogenated polymers in particular is discussed. It is shown that the Auger spectra of halogenated polymers have certain characteristics that permit an assessment of whether a polymeric transfer film has been established by sliding contact. The discussion is general and the concepts should be useful in considering the Auger analysis of any polymer. The polymers chosen for this study are the halogenated polymers polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), and polychlorotrifluorethylene (PCTFE).

Real-time, high frequency (1 Hz), in situ measurement of HCl and HF gases in volcanic plumes with a novel cavity-enhanced, laser-based instrument

NASA Astrophysics Data System (ADS)

Kelly, P. J.; Sutton, A. J.; Elias, T.; Kern, C.; Clor, L. E.; Baer, D. S.

2017-12-01

Primary magmatic halogen-containing gases (HCl, HF, HBr, HI in characteristic order of abundance) are of great interest for volcano monitoring and research because, in general, they are more soluble in magma than other commonly-monitored volcanic volatiles (e.g. CO2, SO2, H2S) and thereby can offer unique insights into shallow magmatic processes. Nevertheless, difficulties in obtaining observations of primary volcanic halogens in gas plumes with traditional methods (e.g. direct sampling, Open-Path Fourier Transform Infrared spectroscopy, filter packs) have limited the number of observations reported worldwide, especially from explosive arc volcanoes. With this in mind, the USGS and Los Gatos Research, Inc. collaborated to adapt a commercially-available industrial in situ HCl-HF analyzer for use in airborne and ground-based measurements of volcanic gases. The new, portable instrument is based around two near-IR tunable diode lasers and uses a vibration-tolerant, enhanced-cavity approach that is well-suited for rugged field applications and yields fast (1 Hz) measurements with a wide dynamic range (0 -2 ppm) and sub-ppb precision (1σ: HCl: <0.4 ppb; HF: <0.1 ppb). In spring 2017 we conducted field tests at Kīlauea Volcano, Hawaii, to benchmark the performance of the new instrument and to compare it with an accepted method for halogen measurements (OP-FTIR). The HCl-HF instrument was run in parallel with a USGS Multi-GAS to obtain in situ H2O-CO2-SO2-H2S-HCl-HF plume compositions. The results were encouraging and quasi-direct comparisons of the in situ and remote sensing instruments showed good agreement (e.g. in situ SO2/HCl = 72 vs. OP-FTIR SO2/HCl = 88). Ground-based and helicopter-based measurements made 0 - 12 km downwind from the vent (plume age 0 - 29 minutes) show that plume SO2/HCl ratios increase rapidly from 60 to 300 around the plume edges, possibly due to uptake of HCl onto aerosols.

Miniaturized Laser Heterodyne Radiometer (LHR) for Measurements of Greenhouse Gases in the Atmospheric Column

NASA Technical Reports Server (NTRS)

Steel, Emily; McLinden, Matthew

2012-01-01

This passive laser heterodyne radiometer (LHR) instrument simultaneously measures multiple trace gases in the atmospheric column including carbon dioxide (CO2) and methane (CH4), and resolves their concentrations at different altitudes. This instrument has been designed to operate in tandem with the passive aerosol sensor currently used in AERONET (an established network of more than 450 ground aerosol monitoring instruments worldwide). Because aerosols induce a radiative effect that influences terrestrial carbon exchange, simultaneous detection of aerosols with these key carbon cycle gases offers a uniquely comprehensive measurement approach. Laser heterodyne radiometry is a technique for detecting weak signals that was adapted from radio receiver technology. In a radio receiver, a weak input signal from a radio antenna is mixed with a stronger local oscillator signal. The mixed signal (beat note, or intermediate frequency) has a frequency equal to the difference between the input signal and the local oscillator. The intermediate frequency is amplified and sent to a detector that extracts the audio from the signal. In the LHR instrument described here, sunlight that has undergone absorption by the trace gas is mixed with laser light at a frequency matched to a trace gas absorption feature in the infrared (IR). Mixing results in a beat signal in the RF (radio frequency) region that can be related to the atmospheric concentration. For a one-second integration, the estimated column sensitivities are 0.1 ppmv for CO2, and <1 ppbv for CH4. In addition to producing a standalone ground measurement product, this instrument could be used to calibrate/validate four Earth observing missions: ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons), OCO-2 (Orbiting Carbon Observatory), OCO-3, and GOSAT (Greenhouse gases Observational SATellite). The only network that currently measures CO2 and CH4 in the atmospheric column is TCCON (Total Carbon Column

Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.

The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared tomore » the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σ AX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.« less

Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

DOE PAGES

Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.; ...

2014-12-05

The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared tomore » the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σ AX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.« less

40 CFR 721.8875 - Substituted halogenated pyridinol.

Code of Federal Regulations, 2012 CFR

2012-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1273) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8750 - Halogenated substituted pyridine.

Code of Federal Regulations, 2010 CFR

2010-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8875 - Substituted halogenated pyridinol.

Code of Federal Regulations, 2013 CFR

2013-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1273) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8850 - Disubstituted halogenated pyridinol.

Code of Federal Regulations, 2011 CFR

2011-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1274) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8850 - Disubstituted halogenated pyridinol.

Code of Federal Regulations, 2012 CFR

2012-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1274) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8750 - Halogenated substituted pyridine.

Code of Federal Regulations, 2012 CFR

2012-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8850 - Disubstituted halogenated pyridinol.

Code of Federal Regulations, 2013 CFR

2013-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1274) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8875 - Substituted halogenated pyridinol.

Code of Federal Regulations, 2014 CFR

2014-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1273) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8750 - Halogenated substituted pyridine.

Code of Federal Regulations, 2011 CFR

2011-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8875 - Substituted halogenated pyridinol.

Code of Federal Regulations, 2010 CFR

2010-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1273) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8750 - Halogenated substituted pyridine.

Code of Federal Regulations, 2013 CFR

2013-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8875 - Substituted halogenated pyridinol.

Code of Federal Regulations, 2011 CFR

2011-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1273) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8850 - Disubstituted halogenated pyridinol.

Code of Federal Regulations, 2014 CFR

2014-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1274) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8750 - Halogenated substituted pyridine.

Code of Federal Regulations, 2014 CFR

2014-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses described...

40 CFR 721.8850 - Disubstituted halogenated pyridinol.

Code of Federal Regulations, 2010 CFR

2010-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses... pyridinol (PMN P-88-1274) is subject to reporting under this section for the significant new uses described...

Iodine(III) Derivatives as Halogen Bonding Organocatalysts.

PubMed

Heinen, Flemming; Engelage, Elric; Dreger, Alexander; Weiss, Robert; Huber, Stefan M

2018-03-26

Hypervalent iodine(III) derivatives are known as versatile reagents in organic synthesis, but there is only one previous report on their use as Lewis acidic organocatalysts. Herein, we present first strong indications for the crucial role of halogen bonding in this kind of catalyses. To this end, the solvolysis of benzhydryl chloride and the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone served as benchmark reactions for halide abstraction and the activation of neutral compounds. Iodolium compounds (cyclic diaryl iodonium species) were used as activators or catalysts, and we were able to markedly reduce or completely switch off their activity by sterically blocking one or two of their electrophilic axes. Compared with previously established bidentate cationic halogen bond donors, the monodentate organoiodine derivatives used herein are at least similarly active (in the Diels-Alder reaction) or even decidedly more active (in benzhydryl chloride solvolysis). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Derivatization in gas chromatographic determination of phenol and aniline traces in aqueous media

NASA Astrophysics Data System (ADS)

Gruzdev, I. V.; Zenkevich, I. G.; Kondratenok, B. M.

2015-06-01

Substituted anilines and phenols are the most common hydrophilic organic environmental toxicants. The principles of gas chromatographic determination of trace amounts of these compounds in aqueous media at concentrations <=0.1 μg litre-1 based on synthesis of their derivatives (derivatization) directly in the aqueous phase are considered. Conversion of relatively hydrophilic analytes into more hydrophobic derivatives makes it possible to achieve such low detection limits and optimize the protocols of extractive preconcentration and selective chromatographic detection. Among the known reactions, this condition is best met by electrophilic halogenation of compounds at the aromatic moiety. The bibliography includes 177 references.

Analysis of Trace Gas Mixtures Using an External Cavity Quantum Cascade Laser Sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Mark C.; Taubman, Matthew S.; Brumfield, Brian E.

2015-07-01

We measure and analyze mixtures of trace gases at ppb-ppm levels using an external cavity quantum cascade laser sensor with a 1-second response time. Accurate spectral fits are obtained in the presence of overlapping spectra.

Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

PubMed Central

2013-01-01

This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4′-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results. PMID:24215390

Combined diffraction and density functional theory calculations of halogen-bonded cocrystal monolayers.

PubMed

Sacchi, Marco; Brewer, Adam Y; Jenkins, Stephen J; Parker, Julia E; Friščić, Tomislav; Clarke, Stuart M

2013-12-03

This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4'-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results.

40 CFR 721.8700 - Halogenated alkyl pyridine.

Code of Federal Regulations, 2013 CFR

2013-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

40 CFR 721.8700 - Halogenated alkyl pyridine.

Code of Federal Regulations, 2012 CFR

2012-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

[Emission and control of gases and odorous substances from animal housing and manure depots].

PubMed

Hartung, J

1992-02-01

Agricultural animal production in increasingly regarded as a source of gases which are both aggravating and ecologically harmful. An overview of the origin, number and quantity of trace gases emitted from animal housing and from manure stores is presented and possible means of preventing or reducing them are discussed. Of the 136 trace gases in the air of animal houses, odorous substances, ammonia and methane are most relevant to the environment. The role played by the remaining gases is largely unknown. Quantitative information is available for 23 gases. The gases are emitted principally from freshly deposited and stored faeces, from animal feed and from the animals themselves. Future work should determine sources and quantities of the gases emitted from animal housing more precisely and should aim to investigate the potential of these gases to cause damage in man, animals and environment. Odorous substances have an effect on the area immediately surrounding the animal housing. They can lead to considerable aggravation in humans. For years, VDI1 guidelines (3471/72), which prescribe distances between residential buildings and animal housing, have been valuable in preventing odour problems of this kind. Coverings are suitable for outside stores. The intensity of the odour from animal housing waste air increases from cattle through to hens and pigs; it is also further affected by the type of housing, the age of the animals and the purpose for which they are being kept. Methods of cleaning waste air (scrubbers/biofilters) are available for problematic cases. The need for guidelines to limit emissions from individual outside manure stores (lagoons) is recognised. Total ammonia emissions from animal production in the Federal Republic of Germany (up to 1989) are estimated at approximately 300,000 to 600,000 t/year. There is a shortage of satisfactory and precise research on the extent of emissions, in particular on those from naturally ventilated housing. It is

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

NASA Astrophysics Data System (ADS)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Rapid chemical evolution of tropospheric volcanic emissions from Redoubt Volcano, Alaska, based on observations of ozone and halogen-containing gases

NASA Astrophysics Data System (ADS)

Kelly, Peter J.; Kern, Christoph; Roberts, Tjarda J.; Lopez, Taryn; Werner, Cynthia; Aiuppa, Alessandro

2013-06-01

We report results from an observational and modeling study of reactive chemistry in the tropospheric plume emitted by Redoubt Volcano, Alaska. Our measurements include the first observations of Br and I degassing from an Alaskan volcano, the first study of O3 evolution in a volcanic plume, as well as the first detection of BrO in the plume of a passively degassing Alaskan volcano. This study also represents the first detailed spatially-resolved comparison of measured and modeled O3 depletion in a volcanic plume. The composition of the plume was measured on June 20, 2010 using base-treated filter packs (for F, Cl, Br, I, and S) at the crater rim and by an instrumented fixed-wing aircraft on June 21 and August 19, 2010. The aircraft was used to track the chemical evolution of the plume up to ~ 30 km downwind (2 h plume travel time) from the volcano and was equipped to make in situ observations of O3, water vapor, CO2, SO2, and H2S during both flights plus remote spectroscopic observations of SO2 and BrO on the August 19th flight. The airborne data from June 21 reveal rapid chemical O3 destruction in the plume as well as the strong influence chemical heterogeneity in background air had on plume composition. Spectroscopic retrievals from airborne traverses made under the plume on August 19 show that BrO was present ~ 6 km downwind (20 min plume travel time) and in situ measurements revealed several ppbv of O3 loss near the center of the plume at a similar location downwind. Simulations with the PlumeChem model reproduce the timing and magnitude of the observed O3 deficits and suggest that autocatalytic release of reactive bromine and in-plume formation of BrO were primarily responsible for the observed O3 destruction in the plume. The measurements are therefore in general agreement with recent model studies of reactive halogen formation in volcanic plumes, but also show that field studies must pay close attention to variations in the composition of ambient air

Rapid chemical evolution of tropospheric volcanic emissions from Redoubt Volcano, Alaska, based on observations of ozone and halogen-containing gases

USGS Publications Warehouse

Werner, Cynthia A.; Kelly, Peter; Kern, Christoph; Roberts, T.J.; Aluppe, A.

2013-01-01

We report results from an observational and modeling study of reactive chemistry in the tropospheric plume emitted by Redoubt Volcano, Alaska. Our measurements include the first observations of Br and I degassing from an Alaskan volcano, the first study of O3 evolution in a volcanic plume, as well as the first detection of BrO in the plume of a passively degassing Alaskan volcano. This study also represents the first detailed spatially-resolved comparison of measured and modeled O3 depletion in a volcanic plume. The composition of the plume was measured on June 20, 2010 using base-treated filter packs (for F, Cl, Br, I, and S) at the crater rim and by an instrumented fixed-wing aircraft on June 21 and August 19, 2010. The aircraft was used to track the chemical evolution of the plume up to ~ 30 km downwind (2 h plume travel time) from the volcano and was equipped to make in situ observations of O3, water vapor, CO2, SO2, and H2S during both flights plus remote spectroscopic observations of SO2 and BrO on the August 19th flight. The airborne data from June 21 reveal rapid chemical O3 destruction in the plume as well as the strong influence chemical heterogeneity in background air had on plume composition. Spectroscopic retrievals from airborne traverses made under the plume on August 19 show that BrO was present ~ 6 km downwind (20 min plume travel time) and in situ measurements revealed several ppbv of O3 loss near the center of the plume at a similar location downwind. Simulations with the PlumeChem model reproduce the timing and magnitude of the observed O3 deficits and suggest that autocatalytic release of reactive bromine and in-plume formation of BrO were primarily responsible for the observed O3 destruction in the plume. The measurements are therefore in general agreement with recent model studies of reactive halogen formation in volcanic plumes, but also show that field studies must pay close attention to variations in the composition of

Characterization of atmospheric trace gases and particulate matter in Hangzhou, China

NASA Astrophysics Data System (ADS)

Zhang, Gen; Xu, Honghui; Qi, Bing; Du, Rongguang; Gui, Ke; Wang, Hongli; Jiang, Wanting; Liang, Linlin; Xu, Wanyun

2018-02-01

The Yangtze River Delta (YRD) is one of the most densely populated regions in China with severe air quality issues that have not been fully understood. Thus, in this study, based on 1-year (2013) continuous measurement at a National Reference Climatological Station (NRCS, 30.22° N, 120.17° E; 41.7 m a.s.l.) in the center of Hangzhou in the YRD, we investigated the seasonal characteristics, interspecies relationships, and the local emissions and the regional potential source contributions of trace gases (including O3, NOx, NOy, SO2, and CO) and particulate matter (PM2.5 and PM10). Results revealed that severe two-tier air pollution (photochemical and haze pollution) occurred in this region, with frequent exceedances in O3 (38 days) and PM2.5 (62 days). O3 and PM2.5 both exhibited distinct seasonal variations with reversed patterns: O3 reaching a maximum in warm seasons (May and July) but PM2.5 reaching a maximum in cold seasons (November to January). The overall results from interspecies correlation indicated a strong local photochemistry favoring the O3 production under a volatile organic compound (VOC)-limited regime, whereas it moved towards an optimum O3 production zone during warm seasons, accompanied by the formation of secondary fine particulates under high O3. The emission maps of PM2.5, CO, NOx, and SO2 demonstrated that local emissions were significant for these species on a seasonal scale. The contributions from the regional transport among inland cities (Zhejiang, Jiangsu, Anhui, and Jiangxi Province) on a seasonal scale were further confirmed to be crucial to air pollution at the NRCS site by using backward trajectory simulations. Air masses transported from the offshore areas of the Yellow Sea, East Sea, and South Sea were also found to be highly relevant to the elevated O3 at the NRCS site through the analysis of potential source contribution function (PSCF). Case studies of photochemical pollution (O3) and haze (PM2.5) episodes both suggested the

Emission factors of fine particles, carbonaceous aerosols and traces gases from road vehicles: Recent tests in an urban tunnel in the Pearl River Delta, China

NASA Astrophysics Data System (ADS)

Zhang, Yanli; Wang, Xinming; Li, Guanghui; Yang, Weiqiang; Huang, Zhonghui; Zhang, Zhou; Huang, Xinyu; Deng, Wei; Liu, Tengyu; Huang, Zuzhao; Zhang, Zhanyi

2015-12-01

Motor vehicles contribute primarily and secondarily to air quality problems due to fine particle (PM2.5) and ozone (O3) pollution in China's megacities. Characterizing vehicle emission with the rapid change of vehicle numbers and fleet compositions is vital for both bottom-up emission survey and top-down source apportioning. To obtain emission factors (EFs) of PM2.5, carbonaceous aerosols and trace gases for road vehicles, in urban Guangzhou we conducted a field campaign in 2014 in the Zhujiang Tunnel, a heavily burdened tunnel with about 40,000 motor vehicles passing through each of its two separated bores per day. PM2.5 and volatile organic compounds (VOCs) were sampled for offline analysis while trace gases including SO2, NOx and CO were measured online and in situ. An eddy covariance system with an integrated 3-D sonic anemometer was also adopted to measure CO2 and winds inside the tunnel. We recorded an average fleet composition of 61% light-duty gasoline vehicles (LDVs) + 12% heavy-duty diesel vehicles (HDVs) + 27% liquefied petroleum gas vehicles (LPGVs), and EFs of 82.7 ± 28.3, 19.3 ± 4.7 and 13.3 ± 3.3 mg veh-1 km-1, respectively, for PM2.5, organic carbon (OC) and elemental carbon (EC). These EFs were respectively 23.4%, 18.3% and 72.3% lower when compared to that measured in the same tunnel in 2004. EFs of PM2.5, OC and EC were higher at night time (148 ± 126, 29 ± 24 and 21 ± 18 mg veh-1 km-1, respectively) due to significantly elevated fractions of HDVs in the traffic fleets. An average ratio of OC to EC 1.45 from this tunnel study was much higher than that of ∼0.5 in previous tunnel studies. The EFs of SO2, NOx, CO, CO2 and NMHCs for road traffic were also obtained from our tunnel tests, and they were 20.7 ± 2.9, (1.29 ± 0.2)E+03, (3.10 ± 0.68)E+03, (3.90 ± 0.49)E+05, and 448 ± 39 mg veh-1 km-1, respectively.

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

PubMed

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Influence of Trace Gases Absorption on Differential Ring Cross Sections

NASA Astrophysics Data System (ADS)

Han, Dong; Zhao, Keyi

2017-04-01

The Ring effect refers to the filling in of Fraunhofer lines, which is known as solar absorption lines, caused almost entirely by rotational Raman scattering. The rotational Raman scattering by N2 and O2 in the atmosphere is the main factor that leads to Ring effect. The Ring effect is one significant limitation to the accuracy of the retrieval of trace gas constituents in atmosphere, while using satellite data with Differential Optical Absorption Spectroscopy technique. In this study, firstly the solar spectrum is convolved with rotational Raman cross sections of atmosphere, which is calculated with rotational Raman cross sections of N2 and O2, divided by the original solar spectrum, with a cubic polynomial subtracted off, to create differential Ring spectrum Ring1. Secondly, the Ring effect for pure Raman scattering of the Fraunhofer spectrum plus the contribution from interference by terrestrial absorption which always comes from a kind of trace gas (e.g., O3) are derived. To allow for more generality, the optically thin term as well as the next term in the expansion for the Beer-Lambert law are calculated.Ring1, Ring2, and Ring3are the Fraunhofer only, 1st terrestrial correction, and 2nd terrestrial correction for DOAS fitting.

Trace gas emissions from burning Florida wetlands

NASA Technical Reports Server (NTRS)

Cofer, Wesley R., III; Levine, Joel S.; Lebel, Peter J.; Winstead, Edward L.; Koller, Albert M., Jr.; Hinkle, C. Ross

1990-01-01

Measurements of biomass burn-produced trace gases were obtained using a helicopter at low altitudes above burning Florida wetlands on November 9, 1987, and from both helicopter and light-aircraft samplings on November 7, 1988. Carbon dioxide normalized emission ratios for carbon monoxide, hydrogen, methane, total nonmethane hydrocarbons, and nitrous oxide were obtained over burning graminoid wetlands consisting primarily of Spartina bakeri and Juncus roemerianus. Some interspersed scrub oak and saw palmetto were also burned. No significant differences were observed in the emission ratios determined for these gases from samples collected over flaming, mixed, and smoldering phases of combustion during the 1987 fire. Combustion-categorized differences in emission ratios were small for the 1988 fire. Combustion efficiency was relatively good (low emission ratios for reduced gases) for both fires. It is believed that the consistently low emission ratios were a unique result of graminoid wetlands fires, in which the grasses and rushes burned rapidly down to standing water and were quickly extinguished. Consequently, the efficiency of the combustion was good and the amount and duration of smoldering combustion was greatly deminished.

Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

EPA Science Inventory

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

Comparing colour discrimination and proofreading performance under compact fluorescent and halogen lamp lighting.

PubMed

Mayr, Susanne; Köpper, Maja; Buchner, Axel

2013-01-01

Legislation in many countries has banned inefficient household lighting. Consequently, classic incandescent lamps have to be replaced by more efficient alternatives such as halogen and compact fluorescent lamps (CFL). Alternatives differ in their spectral power distributions, implying colour-rendering differences. Participants performed a colour discrimination task - the Farnsworth-Munsell 100 Hue Test--and a proofreading task under CFL or halogen lighting of comparable correlated colour temperatures at low (70 lx) or high (800 lx) illuminance. Illuminance positively affected colour discrimination and proofreading performance, whereas the light source was only relevant for colour discrimination. Discrimination was impaired with CFL lighting. There were no differences between light sources in terms of self-reported physical discomfort and mood state, but the majority of the participants correctly judged halogen lighting to be more appropriate for discriminating colours. The findings hint at the colour-rendering deficiencies associated with energy-efficient CFLs. In order to compare performance under energy-efficient alternatives of classic incandescent lighting, colour discrimination and proofreading performance was compared under CFL and halogen lighting. Colour discrimination was impaired under CFLs, which hints at the practical drawbacks associated with the reduced colour-rendering properties of energy-efficient CFLs.

Canonical partition functions: ideal quantum gases, interacting classical gases, and interacting quantum gases

NASA Astrophysics Data System (ADS)

Zhou, Chi-Chun; Dai, Wu-Sheng

2018-02-01

In statistical mechanics, for a system with a fixed number of particles, e.g. a finite-size system, strictly speaking, the thermodynamic quantity needs to be calculated in the canonical ensemble. Nevertheless, the calculation of the canonical partition function is difficult. In this paper, based on the mathematical theory of the symmetric function, we suggest a method for the calculation of the canonical partition function of ideal quantum gases, including ideal Bose, Fermi, and Gentile gases. Moreover, we express the canonical partition functions of interacting classical and quantum gases given by the classical and quantum cluster expansion methods in terms of the Bell polynomial in mathematics. The virial coefficients of ideal Bose, Fermi, and Gentile gases are calculated from the exact canonical partition function. The virial coefficients of interacting classical and quantum gases are calculated from the canonical partition function by using the expansion of the Bell polynomial, rather than calculated from the grand canonical potential.

Generalized Forchheimer Flows of Isentropic Gases

NASA Astrophysics Data System (ADS)

Celik, Emine; Hoang, Luan; Kieu, Thinh

2018-03-01

We consider generalized Forchheimer flows of either isentropic gases or slightly compressible fluids in porous media. By using Muskat's and Ward's general form of the Forchheimer equations, we describe the fluid dynamics by a doubly nonlinear parabolic equation for the appropriately defined pseudo-pressure. The volumetric flux boundary condition is converted to a time-dependent Robin-type boundary condition for this pseudo-pressure. We study the corresponding initial boundary value problem, and estimate the L^∞ and W^{1,2-a} (with 0trace theorem and an appropriate modification of Moser's iteration.

Observations of tropospheric trace gases and meteorology in rural Virginia using an unattended monitoring system: Hurricane Hugo (1989), A case study

NASA Astrophysics Data System (ADS)

Doddridge, Bruce G.; Dickerson, Russell R.; Holland, Joshua Z.; Cooper, James N.; Wardell, R. Glenn; Poulida, Olga; Watkins, James G.

1991-05-01

Tropospheric trace gases such as ozone and reactive nitrogen compounds exert a strong influence on global climate, but observations of these species are limited by the necessity of having a trained observer on site to monitor instruments. A technique using modern communications technology has been developed to transport and review data collected at a remote site. The site was equipped with a PAM II station and satellite data link so that raw, real-time data and equipment status were available for inspection readily on a workstation at the University of Maryland campus through a combination of wide and local area networks. CO, NO, NOy, O3, UV radiative flux, and meteorological parameters were measured in rural Virginia for a full year. The cleanest air observed over the year was associated with the passage of Hurricane Hugo over the mid-Atlantic region on September 22, 1989. Hourly average data for concentrations of CO, NOy, and O3 observed during this particular case study were as low as 90 ppbv, 570 pptv, and 11 ppbv, respectively. Within this period, daytime NO was highly variable, ranging between the detection limit of the instrument, ˜ 20 pptv, and 2.4 ppbv. These concentrations are well below the hourly concentration average at this site for these species during September 1989. Equivalent potential temperature, θe, in conjunction with the trace gas concentrations and geostrophic back-trajectories, illustrates how this hurricane influenced air parcel history; observed concentrations of CO and NOy increased with the time the air parcel spent over land. Observations at this site were consistent with current hurricane models based on mean soundings and aircraft flights. Hurricanes over land also appear to redistribute air vertically throughout the troposphere, creating the potential for substantial post-storm tropospheric column O3 increase.

Virucidal properties of metal oxide nanoparticles and their halogen adducts.

PubMed

Häggström, Johanna; Balyozova, Denitza; Klabunde, Kenneth J; Marchin, George

2010-04-01

Selected metal oxide nanoparticles are capable of strongly adsorbing large amounts of halogens (Cl(2), Br, I(2)) and mixed halogens. These solid adducts are relatively stable thermally, and they can be stored for long periods. However, in the open environment, they are potent biocides. Herein are described studies with a number of bacteriophage MS2, phiX174, and PRD-1 (virus examples). PRD-1 is generally more resistant to chemical disinfection, but in this paper it is shown to be very susceptible to selected interhalogen and iodine adducts of CeO(2), Al(2)O(3), and TiO(2) nanoparticles. Overall, the halogen adducts of TiO(2) and Al(2)O(3) were most effective. The mechanism of disinfection by these nanoparticles is not completely clear, but could include abrasive properties, as well as oxidative powers. A hypothesis that nanoparticles damage virons or stick to them and prevent binding to the host cell is a consideration that needs to be explored. Herein are reported comparative biocidal activities of a series of adducts and electron microscope images of before and after treatment.

Importance of reactive halogens in the tropical marine atmosphere using WRF-chem

NASA Astrophysics Data System (ADS)

Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; Apel, Eric; Saiz-Lopez, Alfonso; von Glasow, Roland

2017-04-01

Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens participate in catalytic reaction cycles that efficiently destroy O3, change the HOX and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. Up to 34% of O3 loss in the tropical East Pacific is due to I and Br combined. Recent studies have highlighted the key role that heterogeneous chemistry plays in explaining observations of BrO and IO abundances in the tropical troposphere. The main objective of this study is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. Our reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. Heterogeneous recycling reactions involving sea-salt aerosol and other particles have been included into the model, along with oceanic emissions of important OVOCs and halocarbons. Sea surface emissions of inorganic iodine are calculated using the parameterisation of Carpenter et al., 2013. Focusing on TORERO observations from the ships and a selected number of flights we present the tropospheric impacts of halogens (BrO, IO) in the tropospheric chemistry of relevant species (O3, OH and OVOCS). Sensitivity runs are made in order to study the impact of heterogeneous chemistry in the iodine and bromine species partitioning. A comparison between the online calculation of Very Short Lived Halocarbons (VSLH) oceanic emissions with prescribed oceanic emissions is

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

PubMed

Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

2016-07-01

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

Fourier Transform Spectroscopy of two trace gases namely Methane and Carbon monoxide for planetary and atmospheric research application

NASA Astrophysics Data System (ADS)

Hashemi, R.; Dudaryonok, A. S.; Lavrentieva, N. N.; Vandaele, A. C.; Vander Auwera, J.; Tyuterev, AV Nikitin G., VI; Sung, K.; Smith, M. A. H.; Devi, V. M.; Predoi-Cross, A.

2017-02-01

Two atmospheric trace gases, namely methane and carbon monoxide have been considered in this study. Fourier transform absorption spectra of the 2-0 band of 12C16O mixed with CO2 have been recorded at total pressures from 156 to 1212 hPa and at 4 different temperatures between 240 K and 283 K. CO2 pressure-induced line broadening and line shift coefficients, and the associated temperature dependence have been measured in an multi-spectrum non-linear least squares analysis using Voigt profiles with an asymmetric profile due to line mixing. The measured CO2-broadening and CO2-shift parameters were compared with theoretical values, calculated by collaborators. In addition, the CO2-broadening and shift coefficients have been calculated for individual temperatures using the Exponential Power Gap (EPG) semi-empirical method. We also discuss the retrieved line shape parameters for Methane transitions in the spectral range known as the Methane Octad. We used high resolution spectra of pure methane and of dilute mixtures of methane in dry air, recorded with high signal to noise ratio at temperatures between 148 K and room temperature using the Bruker IFS 125 HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California. Theoretical calculations for line parameters have been performed and the results are compared with the previously published values and with the line parameters available in the GEISA2015 [1] and HITRAN2012 [2] databases.

One year observations of atmospheric reactive gases (O3, CO, NOx, SO2) at Jang Bogo base in Terra Nova Bay, Antarctica

NASA Astrophysics Data System (ADS)

Siek Rhee, Tae; Seo, Sora

2016-04-01

Antarctica is a remote area surrounded by the Southern Ocean and far from the influence of human activities, giving us unique opportunity to investigate the background variation of trace gases which are sensitive to the human activities. Korean Antarctic base, Jang Bogo, was established as a unique permanent overwintering base in Terra Nova Bay in February, 2014. One year later, we installed a package of instruments to monitor atmospheric trace gases at the base, which includes long-lived greenhouse gases, CO2, CH4, and N2O, and reactive gases, O3, CO, NOx, and SO2. The atmospheric chemistry observatory, where these scientific instruments were installed, is located ca. 1 km far from the main building and power plant, minimizing the influence of pollution that may come from the operation of the base. Here we focus on the reactive gases measured in-situ at the base; O3 displays a typical seasonal variation with high in winter and low in summer with seasonal amplitude of ~18 ppb, CO was high in September at ~56 ppb, probably implying the invasion of lower latitude air mass with biomass burning, and low in late summer due to photochemical oxidation. NO did not show clear seasonal variation, but SO2 reveals larger values in summer than in winter. We will discuss potential atmospheric processes behind these first observations of reactive gases in Terra Nova Bay, Antarctica.

Modern inhalation anesthetics: Potent greenhouse gases in the global atmosphere

NASA Astrophysics Data System (ADS)

Vollmer, Martin K.; Rhee, Tae Siek; Rigby, Matt; Hofstetter, Doris; Hill, Matthias; Schoenenberger, Fabian; Reimann, Stefan

2015-03-01

Modern halogenated inhalation anesthetics undergo little metabolization during clinical application and evaporate almost completely to the atmosphere. Based on their first measurements in a range of environments, from urban areas to the pristine Antarctic environment, we detect a rapid accumulation and ubiquitous presence of isoflurane, desflurane, and sevoflurane in the global atmosphere. Over the past decade, their abundances in the atmosphere have increased to global mean mole fractions in 2014 of 0.097ppt, 0.30ppt, and 0.13ppt (parts per trillion, 10-12, in dry air), respectively. Emissions of these long-lived greenhouse gases inferred from the observations suggest a global combined release to the atmosphere of 3.1 ± 0.6 million t CO2 equivalent in 2014 of which ≈80% stems from desflurane. We also report on halothane, a previously widely used anesthetic. Its global mean mole fraction has declined to 9.2ppq (parts per quadrillion, 10-15) by 2014. However, the inferred present usage is still 280 ±120t yr-1.

Rapid and reliable determination of the halogenating peroxidase activity in blood samples.

PubMed

Flemmig, Jörg; Schwarz, Pauline; Bäcker, Ingo; Leichsenring, Anna; Lange, Franziska; Arnhold, Jürgen

2014-12-15

By combining easy and fast leukocyte enrichment with aminophenyl-fluorescein (APF) staining we developed a method to quickly and specifically address the halogenating activity of the immunological relevant blood heme peroxidases myeloperoxidase and eosinophil peroxidase, respectively. For leukocyte enrichment a two-fold hypotonic lysis procedure of the blood with Millipore water was chosen which represents a cheap, fast and reliable method to diminish the amount of erythrocytes in the samples. This procedure is shown to be suitable both to human and murine blood micro-samples, making it also applicable to small animal experiments with recurring blood sampling. As all types of leukocytes are kept in the sample during the preparation, they can be analysed separately after discrimination during the flow cytometry analysis. This also holds for all heme peroxidase-containing cells, namely neutrophils, eosinophils and monocytes. Moreover additional parameters (e.g. antibody staining) can be combined with the heme peroxidase activity determination to gain additional information about the different immune cell types. Based on previous results we applied APF for specifically addressing the halogenating activity of leukocyte peroxidases in blood samples. This dye is selectively oxidized by the MPO and EPO halogenation products hypochlorous and hypobromous acid. This approach may provide a suitable tool to gain more insights into the immune-physiological role of the halogenating activity of heme peroxidases. Copyright © 2014 Elsevier B.V. All rights reserved.

The 1257 Samalas eruption (Lombok, Indonesia): the single greatest stratospheric gas release of the Common Era.

PubMed

Vidal, Céline M; Métrich, Nicole; Komorowski, Jean-Christophe; Pratomo, Indyo; Michel, Agnès; Kartadinata, Nugraha; Robert, Vincent; Lavigne, Franck

2016-10-10

Large explosive eruptions inject volcanic gases and fine ash to stratospheric altitudes, contributing to global cooling at the Earth's surface and occasionally to ozone depletion. The modelling of the climate response to these strong injections of volatiles commonly relies on ice-core records of volcanic sulphate aerosols. Here we use an independent geochemical approach which demonstrates that the great 1257 eruption of Samalas (Lombok, Indonesia) released enough sulphur and halogen gases into the stratosphere to produce the reported global cooling during the second half of the 13th century, as well as potential substantial ozone destruction. Major, trace and volatile element compositions of eruptive products recording the magmatic differentiation processes leading to the 1257 eruption indicate that Mt Samalas released 158 ± 12 Tg of sulphur dioxide, 227 ± 18 Tg of chlorine and a maximum of 1.3 ± 0.3 Tg of bromine. These emissions stand as the greatest volcanogenic gas injection of the Common Era. Our findings not only provide robust constraints for the modelling of the combined impact of sulphur and halogens on stratosphere chemistry of the largest eruption of the last millennium, but also develop a methodology to better quantify the degassing budgets of explosive eruptions of all magnitudes.

Halogenated Peptides as Internal Standards (H-PINS)

PubMed Central

Mirzaei, Hamid; Brusniak, Mi-Youn; Mueller, Lukas N.; Letarte, Simon; Watts, Julian D.; Aebersold, Ruedi

2009-01-01

As the application for quantitative proteomics in the life sciences has grown in recent years, so has the need for more robust and generally applicable methods for quality control and calibration. The reliability of quantitative proteomics is tightly linked to the reproducibility and stability of the analytical platforms, which are typically multicomponent (e.g. sample preparation, multistep separations, and mass spectrometry) with individual components contributing unequally to the overall system reproducibility. Variations in quantitative accuracy are thus inevitable, and quality control and calibration become essential for the assessment of the quality of the analyses themselves. Toward this end, the use of internal standards cannot only assist in the detection and removal of outlier data acquired by an irreproducible system (quality control) but can also be used for detection of changes in instruments for their subsequent performance and calibration. Here we introduce a set of halogenated peptides as internal standards. The peptides are custom designed to have properties suitable for various quality control assessments, data calibration, and normalization processes. The unique isotope distribution of halogenated peptides makes their mass spectral detection easy and unambiguous when spiked into complex peptide mixtures. In addition, they were designed to elute sequentially over an entire aqueous to organic LC gradient and to have m/z values within the commonly scanned mass range (300–1800 Da). In a series of experiments in which these peptides were spiked into an enriched N-glycosite peptide fraction (i.e. from formerly N-glycosylated intact proteins in their deglycosylated form) isolated from human plasma, we show the utility and performance of these halogenated peptides for sample preparation and LC injection quality control as well as for retention time and mass calibration. Further use of the peptides for signal intensity normalization and retention time

Investigation of mesoscale trace gas distributions across an Arctic tropopause fold affected by gravity wave activity

NASA Astrophysics Data System (ADS)

Woiwode, Wolfgang; Oelhaf, Hermann; Dörnbrack, Andreas; Bramberger, Martina; Diekmann, Christopher; Friedl-Vallon, Felix; Höpfner, Michael; Hoor, Peter; Johansson, Sören; Krause, Jens; Kunkel, Daniel; Orphal, Johannes; Preusse, Peter; Ruhnke, Roland; Schlage, Romy; Schröter, Jennifer; Sinnhuber, Björn-Martin; Ungermann, Jörn; Zahn, Andreas

2017-04-01

Tropopause folds are known of enabling efficient exchange of trace constituents between the stratosphere and troposphere. In particular, the modification of the vertical distributions of radiatively important H2O and other reactive trace gases associated with tropopause folds is relevant for accurate model simulations of the upper troposphere and lower stratosphere composition. During the POLSTRACC/GW-LCYCLE/SALSA flight on 12 January 2016, the HALO (High Altitude LOng range) aircraft crossed twice an extended tropopause fold in the vicinity of the Arctic polar vortex. At the same time, the ECMWF operational analysis shows that the meteorological scenario probed above Italy was accompanied by wide-spread gravity wave activity induced by north-westerly winds. Using high spectral resolution limb-observations by the GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) spectrometer aboard HALO and associated observations, we investigate the vertical distributions of H2O, O3, temperature, and associated parameters across the tropopause fold. In combination with a high-resolution simulation by the ICON-ART (ICOsahedral Nonhydrostatic- Aerosol and Reactive Trace gases) model, we search for indications for irreversible trace gas exchange between the stratosphere and troposphere and the potential influence of gravity waves.

Syntheses of halogen derivatives of L-tryptophan, L-tyrosine and L-phenylalanine labeled with hydrogen isotopes.

PubMed

Pająk, Małgorzata; Pałka, Katarzyna; Winnicka, Elżbieta; Kańska, Marianna

2016-01-01

Halogenated, labeled with tritium and doubly with deuterium and tritium, derivatives of L-tryptophan, i.e. 5'-bromo-[2-(3)H]-, 5'-bromo-[2-(2)H/(3)H]-, 5'-fluoro-[2-(3)H]-5'-fluoro-[2-(2)H/(3)H]-, 6'-fluoro-[2-(3)H]-, 6'-fluoro-[2-(2)H/(3)H]-L-tryptophan, as well as, L-tyrosine, i.e. 3'-fluoro-[2-(3)H]-, 3'-fluoro-[2-(2)H/(3)H]-, 3'-chloro-[2-(3)H]-, and 3'-chloro-[2-(2)H/(3)H]-L-tyrosine, and also L-phenylalanine, i.e. 2'-fluoro-[(3S)-(3)H]-, 2'-fluoro-[(3S)-(2)H/(3) H]-, 2'-chloro-[(3S)-(3)H]-, 2'-chloro-[(3S)-(2)H/(3)H]-, 4'-chloro-[(3S)-(3)H]-, and 4'-chloro-[(3S)-(2)H/(3)H]-L-phenylalanine were synthesized using enzymatic methods. Isotopomers of L-tryptophan were synthesized by coupling of halogenated indoles with S-methyl-L-cysteine carried out in deuteriated or tritiated incubation media. Labeled halogenated derivatives of L-tyrosine were obtained by the enzymatically supported exchange between halogenated L-tyrosine and isotopic water. Labeled halogenated isotopologues of L-Phe were synthesized by the enzymatic addition of ammonia to halogenated cinnamic acid. As a source of hydrogen tritiated water (HTO) and heavy water (D2O) with addition of HTO were used. Copyright © 2015 John Wiley & Sons, Ltd.

Comparison of halogen, plasma and LED curing units.

PubMed

Nomoto, Rie; McCabe, John F; Hirano, Susumu

2004-01-01

This study evaluated the characteristics of two kinds of recently developed light-curing unit; plasma arc and blue light emitting diodes (LED), in comparison with a conventional tungsten-halogen light-curing unit. The light intensity and spectral distribution of light from these light-curing units, the temperature rise of the bovine enamel surface and the depth of cure of composites exposed to each unit were investigated. The light intensity and depth of cure were determined according to ISO standards. The spectral distributions of emitted light were measured using a spectro-radiometer. The temperature increase induced by irradiation was measured by using a thermocouple. Generally, light intensities in the range 400-515 nm emitted from the plasma arc were greater than those from other types. Light in the UV-A region was emitted from some plasma arc units. The required irradiation times were six to nine seconds for the plasma arc units and 40 to 60 seconds for the LED units to create a depth of cure equal to that produced by the tungsten-halogen light with 20 seconds of irradiation. The temperature increased by increasing the irradiation time for every light-curing unit. The temperature increases were 15 degrees C to 60 degrees C for plasma arc units, around 15 degrees C for a conventional halogen unit and under 10 degrees C for LED units. Both the plasma arc and LED units required longer irradiation times than those recommended by their respective manufacturers. Clinicians should be aware of potential thermal rise and UV-A hazard when using plasma arc units.

Linking genes to ecosystem trace gas fluxes in a large-scale model system

NASA Astrophysics Data System (ADS)

Meredith, L. K.; Cueva, A.; Volkmann, T. H. M.; Sengupta, A.; Troch, P. A.

2017-12-01

Soil microorganisms mediate biogeochemical cycles through biosphere-atmosphere gas exchange with significant impact on atmospheric trace gas composition. Improving process-based understanding of these microbial populations and linking their genomic potential to the ecosystem-scale is a challenge, particularly in soil systems, which are heterogeneous in biodiversity, chemistry, and structure. In oligotrophic systems, such as the Landscape Evolution Observatory (LEO) at Biosphere 2, atmospheric trace gas scavenging may supply critical metabolic needs to microbial communities, thereby promoting tight linkages between microbial genomics and trace gas utilization. This large-scale model system of three initially homogenous and highly instrumented hillslopes facilitates high temporal resolution characterization of subsurface trace gas fluxes at hundreds of sampling points, making LEO an ideal location to study microbe-mediated trace gas fluxes from the gene to ecosystem scales. Specifically, we focus on the metabolism of ubiquitous atmospheric reduced trace gases hydrogen (H2), carbon monoxide (CO), and methane (CH4), which may have wide-reaching impacts on microbial community establishment, survival, and function. Additionally, microbial activity on LEO may facilitate weathering of the basalt matrix, which can be studied with trace gas measurements of carbonyl sulfide (COS/OCS) and carbon dioxide (O-isotopes in CO2), and presents an additional opportunity for gene to ecosystem study. This work will present initial measurements of this suite of trace gases to characterize soil microbial metabolic activity, as well as links between spatial and temporal variability of microbe-mediated trace gas fluxes in LEO and their relation to genomic-based characterization of microbial community structure (phylogenetic amplicons) and genetic potential (metagenomics). Results from the LEO model system will help build understanding of the importance of atmospheric inputs to

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimatesmore » or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.« less

Effect of halogenated impurities on lifetime of organic light emitting diode

NASA Astrophysics Data System (ADS)

Yamawaki, Hayato; Suzuki, Kunihiko; Kubota, Tomohiro; Watabe, Takeyoshi; Ishigaki, Ayumi; Nakamura, Rina; Inoue, Hideko; Nakashima, Harue; Horikoshi, Nozomi; Nowatari, Hiromi; Kataishi, Riho; Hamada, Toshiki; Sasaki, Toshiki; Suzuki, Tsunenori; Seo, Satoshi

2016-09-01

We investigated a correlation between lifetime and the halogen element concentration in an organic light-emitting diode (OLED) and conducted experiments and simulations to discuss degradation mechanisms due to the halogen. OELD is generally formed of high-purity materials. Since the synthesis of high-purity materials takes time and cost, quantitative understanding of the kind, amount, and influence of impurities in OLED devices is expected. The results of combustion ion chromatography show that, if the chlorine concentration in the host material is more than several parts per million, the lifetime of the device is drastically reduced. The chlorine element, which is derived from the chlorinated by-product of the host material, is found to be transferred from the chloride to other materials (e.g., an emissive dopant) according to the results of LC-MS analysis. In addition, the electron transport layer including such impurities is also found to adversely affect the lifetime. The results of TOF-SIMS analysis suggest that the dissociated chlorine element diffuse to the light-emitting layer side when the device is driven. The results of simulations (Gaussian 09) and electrochemical analyses (cyclic voltammetry and electrolysis) reveal that the halogen element is easy to dissociate from halide by excitation or reduction. The halogen element can repeat reactions with the peripheral materials by excitation or reduction and cause damages, e.g., generate radicals or further reaction products due to the radicals. The results of simulation suggest that, such compounds have low energy level and become quenchers.

Volatile halogenated hydrocarbons in foods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyahara, Makoto; Toyoda, Masatake; Saito, Yukio

1995-02-01

Volatile halogenated organic compounds were determined in foods. Statistical treatment of the data for 13 sampled from 20 families living in suburban Tokyo (Saitama prefecture) indicated that the foods were contaminated by water pollution and/or substances introduced by the process of food production. Butter and margarine were contaminated by chlorinated ethylene, ethane, and related compounds released by dry cleaning and other operations. Soybean sprouts and tofu (soybean curd) contained chloroform and related trihalomethanes absorbed during the production process. 27 refs., 6 figs., 5 tabs.

Temperature analysis during bonding of brackets using LED or halogen light base units.

PubMed

Silva, Paulo César Gomes; De Fátima Zanirato Lizarelli, Rosane; Moriyama, Lílian Tan; De Toledo Porto Neto, Sizenando; Bagnato, Vanderlei Salvador

2005-02-01

The purpose of our investigation is to compare the intrapulpal temperature changes following blue LED system and halogen lamp irradiation at the enamel surface of permanent teeth. The fixation of brackets using composite resin is more comfortable and faster when using a photo-curable composite. Several light sources can be used: halogens, arc plasma, lasers, and recently blue LED systems. An important aspect to be observed during such a procedures is the temperature change. In this study, we have used nine human extracted permanent teeth: three central incisors, three lateral incisors, and three canines. Teeth were exposed to two light sources: blue LED system (preliminary commercial model LEC 470-II) and halogen lamp (conventional photo-cure equipment). The surface of teeth was exposed for 20, 40, and 60 sec at the buccal and lingual enamel surface with an angle of 45 degrees. Temperature values measured by a thermistor placed at pulpar chamber were read in time intervals of 1 sec. We obtained plots showing the temperature evolution as a function of time for each experiment. There is a correlation between heating quantity and exposition time of light source: with increasing exposition time, heating increases into the pulpal chamber. The halogen lamp showed higher heating than the LED system, which showed a shorter time of cooling than halogen lamp. The blue LED system seems like the indicated light source for photo-cure of composite resin during the bonding of brackets. The fixation of brackets using composite resin is more comfortable and faster when using a photo-curable composite. Blue LED equipment did not heat during its use. This could permit a shorter clinical time of operation and better performance.

Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

PubMed

Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

2008-10-30

A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): emissions of trace gases and light-absorbing carbon from wood and dung cooking fires, garbage and crop residue burning, brick kilns, and other sources

NASA Astrophysics Data System (ADS)

Stockwell, Chelsea E.; Christian, Ted J.; Goetz, J. Douglas; Jayarathne, Thilina; Bhave, Prakash V.; Praveen, Puppala S.; Adhikari, Sagar; Maharjan, Rashmi; DeCarlo, Peter F.; Stone, Elizabeth A.; Saikawa, Eri; Blake, Donald R.; Simpson, Isobel J.; Yokelson, Robert J.; Panday, Arnico K.

2016-09-01

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign took place in and around the Kathmandu Valley and in the Indo-Gangetic Plain (IGP) of southern Nepal during April 2015. The source characterization phase targeted numerous important but undersampled (and often inefficient) combustion sources that are widespread in the developing world such as cooking with a variety of stoves and solid fuels, brick kilns, open burning of municipal solid waste (a.k.a. trash or garbage burning), crop residue burning, generators, irrigation pumps, and motorcycles. NAMaSTE produced the first, or rare, measurements of aerosol optical properties, aerosol mass, and detailed trace gas chemistry for the emissions from many of the sources. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared (FTIR) spectroscopy, whole-air sampling (WAS), and photoacoustic extinctiometers (PAX; 405 and 870 nm) based on field work with a moveable lab sampling authentic sources. The primary aerosol optical properties reported include emission factors (EFs) for scattering and absorption coefficients (EF Bscat, EF Babs, in m2 kg-1 fuel burned), single scattering albedos (SSAs), and absorption Ångström exponents (AAEs). From these data we estimate black and brown carbon (BC, BrC) emission factors (g kg-1 fuel burned). The trace gas measurements provide EFs (g kg-1) for CO2, CO, CH4, selected non-methane hydrocarbons up to C10, a large suite of oxygenated organic compounds, NH3, HCN, NOx, SO2, HCl, HF, etc. (up to ˜ 80 gases in all). The emissions varied significantly by source, and light absorption by both BrC and BC was important for many sources. The AAE for dung-fuel cooking fires (4.63 ± 0.68) was significantly higher than for wood-fuel cooking fires (3.01 ± 0.10). Dung-fuel cooking fires also emitted high levels of NH3 (3.00 ± 1.33 g kg-1), organic acids (7.66 ± 6.90 g kg-1), and HCN (2.01 ± 1.25 g kg-1), where the latter could

Analysis of Asian Outflow over the Western Pacific using Observations from Trace-P

NASA Technical Reports Server (NTRS)

Jacob, Daniel J.

2004-01-01

Our analysis of the TRACE-P data focused on answering the following questions: 1) How do anthropogenic sources in Asia contribute to chemical outflow over the western Pacific in spring? 2) How does biomass burning in southeast Asia contribute to this outflow? 3) How can the TRACE-P observations be used to better quantify the sources of environmentally important gases in eastern Asia? Our strategy drew on a combination of data analysis and global 3-D modeling, as described below. We also contributed to the planning and execution of TRACE-P through service as mission scientist and by providing chemical model forecasts in the field.

Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

PubMed

Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

2015-08-03

Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Source regions of stratospheric VSLS in the Indian Ocean

NASA Astrophysics Data System (ADS)

Quack, Birgit; Hepach, Helmke; Atlas, Elliot; Bracher, Astrid; Endres, Sonja; Arevalo-Martinez, Damian; Bange, Hermann; Lennartz, Sinikka; Steinhoff, Tobias; Booge, Dennis; Zarvasky, Alexander; Marandino, Christa; Patey, Matt; Achterberg, Eric; Dengler, Markus; Fiehn, Alina; Tegtmeier, Susann; Krüger, Kirstin

2016-04-01

Halogenated very-short-lived substances (VSLS), which are naturally produced in the ocean, play a significant role in present day ozone depletion, in particular in combination with enhanced stratospheric sulfate aerosol, which is also partly derived from oceanic VSLS. The decline of anthropogenic chlorine in the stratosphere within the 21st century will increase the relative importance of the natural emissions on stratospheric ozone destruction. Especially, oceanic sources and source regions of the compounds need to be better constrained, in order to improve the future prediction. During boreal summer the Asian monsoon circulation transports air masses from the Indian Ocean to the stratosphere, while the contribution of VSLS from this ocean to stratospheric halogen and sulfur is unknown. During the research cruises SO 234/2 and SO 235 in July-August 2014 onboard RV SONNE oceanic and atmospheric halogenated VSLS such as bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) were measured in the subtropical and tropical West Indian Ocean for the first time. Here we present the oceanic sources of the halogenated compounds and their relation to other biogeochemical parameters (short- and longlived trace gases, phytoplankton and nutrients) along the cruise track, which covered coastal, upwelling and open ocean regimes and the Seychelles-Chagos thermocline ridge as important source region for stratospheric bromine.

Source identification and apportionment of halogenated compounds observed at a remote site in East Asia.

PubMed

Li, Shanlan; Kim, Jooil; Park, Sunyoung; Kim, Seung-Kyu; Park, Mi-Kyung; Mühle, Jens; Lee, Gangwoong; Lee, Meehye; Jo, Chun Ok; Kim, Kyung-Ryul

2014-01-01

The sources of halogenated compounds in East Asia associated with stratospheric ozone depletion and climate change are relatively poorly understood. High-precision in situ measurements of 18 halogenated compounds and carbonyl sulfide (COS) made at Gosan, Jeju Island, Korea, from November 2007 to December 2011 were analyzed by a positive matrix factorization (PMF). Seven major industrial sources were identified from the enhanced concentrations of halogenated compounds observed at Gosan and corresponding concentration-based source contributions were also suggested: primary aluminum production explaining 37% of total concentration enhancements, solvent usage of which source apportionment is 25%, fugitive emissions from HCFC/HFC production with 11%, refrigerant replacements (9%), semiconductor/electronics industry (9%), foam blowing agents (6%), and fumigation (3%). Statistical trajectory analysis was applied to specify the potential emission regions for seven sources using back trajectories. Primary aluminum production, solvent usage and fugitive emission sources were mainly contributed by China. Semiconductor/electronics sources were dominantly located in Korea. Refrigerant replacement, fumigation and foam blowing agent sources were spread throughout East Asian countries. The specified potential source regions are consistent with country-based consumptions and emission patterns, verifying the PMF analysis results. The industry-based emission sources of halogenated compounds identified in this study help improve our understanding of the East Asian countries' industrial contributions to halogenated compound emissions.

40 CFR 721.4484 - Halogenated indane (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... into a plastic, resin matrix, or pelletized so humans are not reasonally likely to be exposed. (2) The...

40 CFR 721.4484 - Halogenated indane (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... into a plastic, resin matrix, or pelletized so humans are not reasonally likely to be exposed. (2) The...

40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane, substituted...

40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane, substituted...

Tracing halogen and B cycling in subduction zones based on obducted, subducted and forearc serpentinites of the Dominican Republic.

PubMed

Pagé, Lilianne; Hattori, Keiko

2017-12-19

Serpentinites are important reservoirs of fluid-mobile elements in subduction zones, contributing to volatiles in arc magmas and their transport into the Earth's mantle. This paper reports halogen (F, Cl, Br, I) and B abundances of serpentinites from the Dominican Republic, including obducted and subducted abyssal serpentinites and forearc mantle serpentinites. Abyssal serpentinite compositions indicate the incorporation of these elements from seawater and sediments during serpentinization on the seafloor and at slab bending. During their subduction and subsequent lizardite-antigorite transition, F and B are retained in serpentinites, whilst Cl, Br and I are expelled. Forearc mantle serpentinite compositions suggest their hydration by fluids released from subducting altered oceanic crust and abyssal serpentinites, with only minor sediment contribution. This finding is consistent with the minimal subduction of sediments in the Dominican Republic. Forearc mantle serpentinites have F/Cl and B/Cl ratios similar to arc magmas, suggesting the importance of serpentinite dehydration in the generation of arc magmatism in the mantle wedge.

Novel halogen chemistry in the marine boundary layer

NASA Astrophysics Data System (ADS)

Plane, J. M.; Saiz-Lopez, A.; Shillito, J. A.

2003-12-01

This paper will report the first observations of I2 in the marine boundary layer, made by Differential Optical Absorption (DOAS) spectroscopy during a field campaign at Mace Head (Ireland) in the summer of 2002. Very large I2 concentrations correlating with low tide indicate that the source is emission from macro-algae. Simple scaling suggests that this coastal emission could approach 2 Tg per year, making it a major contribution to the global iodine budget. During the same campaign, DOAS observations were also made of the halogen oxides IO, OIO and BrO. The pulses of IO and BrO that were measured at sunrise are strong evidence for heterogeneous processing on sea-salt aerosol producing high levels of IBr during the night. Simple modelling shows that the observed concentrations of the halogen radicals will play important roles in ozone depletion, the oxidation of dimethyl sulfide, and the formation of new particles in the marine boundary layer.

Combining stable isotope (δ13C) of trace gases and aerobiological data to monitor the entry and dispersion of microorganisms in caves.

PubMed

Garcia-Anton, E; Cuezva, S; Jurado, V; Porca, E; Miller, A Z; Fernandez-Cortes, A; Saiz-Jimenez, C; Sanchez-Moral, S

2014-01-01

Altamira Cave (north of Spain) contains one of the world's most prominent Paleolithic rock art paintings, which are threatened by a massive microbial colonization of ceiling and walls. Previous studies revealed that exchange rates between the cave and the external atmosphere through the entrance door play a decisive role in the entry and transport of microorganisms (bacteria and fungi) and nutrients to the interior of the cave. A spatial-distributed sampling and measurement of carrier (CO2) and trace (CH4) gases and isotopic signal of CO2 (δ(13)C) inside the cave supports the existence of a second connection (active gas exchange processes) with the external atmosphere at or near the Well Hall, the innermost and deepest area of the cave. A parallel aerobiological study also showed that, in addition to the entrance door, there is another connection with the external atmosphere, which favors the transport and increases microorganism concentrations in the Well Hall. This double approach provides a more complete knowledge on cave ventilation and revealed the existence of unknown passageways in the cave, a fact that should be taken into account in future cave management.

Tailoring topological states in silicene using different halogen-passivated Si(111) substrates

NASA Astrophysics Data System (ADS)

Derakhshan, Vahid; Moghaddam, Ali G.; Ceresoli, Davide

2018-03-01

We investigate the band structure and topological phases of silicene embedded on halogenated Si(111) surface using density functional theory calculations. Our results show that the Dirac character of low-energy excitations in silicene is almost preserved in the presence of a silicon substrate passivated by various halogens. Nevertheless, the combined effects of symmetry breaking due to both direct and van der Waals interactions between silicene and the substrate, charge transfer from suspended silicene into the substrate, and, finally, the hybridization which leads to the charge redistribution result in a gap in the spectrum of the embedded silicene. We further take the spin-orbit interaction into account and obtain the resulting modification in the gap. The energy gaps with and without spin-orbit coupling vary significantly when different halogen atoms are used for the passivation of the Si surface, and for the case of iodine, they become on the order of 100 meV. To examine the topological properties, we calculate the projected band structure of silicene from which the Berry curvature and Z2 invariant based on the evolution of Wannier charge centers are obtained. As a key finding, it is shown that silicene on halogenated Si substrates has a topological insulating state which can survive even at room temperature for the substrates with iodine and bromine at the surface. Therefore, these results suggest that we can have a reliable, stable, and robust silicene-based two-dimensional topological insulator using the considered substrates.

Method for selective dehalogenation of halogenated polyaromatic compounds

DOEpatents

Farcasiu, Malvina; Petrosius, Steven C.

1994-01-01

A method for dehalogenating halogenated polyaromatic compounds is provided wherein the polyaromatic compounds are mixed with a hydrogen donor solvent and a carbon catalyst in predetermined proportions, the mixture is maintained at a predetermined pressure, and the mixture is heated to a predetermined temperature and for a predetermined time.