40 CFR 279.53 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2011 CFR

2011-07-01

... does not apply to used oils contaminated with chlorofluorocarbons (CFCs) removed from refrigeration... contaminated with CFCs that have been mixed with used oil from sources other than refrigeration units. [57 FR...

40 CFR 279.53 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2013 CFR

2013-07-01

... does not apply to used oils contaminated with chlorofluorocarbons (CFCs) removed from refrigeration... contaminated with CFCs that have been mixed with used oil from sources other than refrigeration units. [57 FR...

PRN 93-4: Ban on Aerosol Products Containing CFCs and HCFCs under the Clean Air Act

EPA Pesticide Factsheets

This notice alerts pesticide registrants to a rule under the Clean Air Act banning distribution and sale of aerosol and pressurized products, including pesticide products, that contain chlorofluorocarbons (CFCs).

Scientific Assessment of Stratospheric Ozone: 1989, volume 2. Appendix: AFEAS Report

NASA Technical Reports Server (NTRS)

1990-01-01

The results are presented of the Alternative Fluorocarbon Environmental Acceptability Study (AFEAS), which was organized to evaluate the potential effects on the environment of alternate compounds targeted to replace fully halogenated chlorofluorocarbons (CFCs). All relevant current scientific information to determine the environmental acceptability of the alternative fluorocarbons. Special emphasis was placed on: the potential of the compounds to affect stratospheric ozone; their potential to affect tropospheric ozone; their potential to contribute to model calculated global warming; the atmospheric degradation mechanisms of the compounds, in order to identify their products; and the potential environmental effects of the decomposition products. The alternative compounds to be studied were hydrofluorocarbons (HFCs) with one or two carbon atoms and one or more each of fluorine and hydrogen.

76 FR 59144 - Novartis Pharmaceuticals Corp. et al.; Withdrawal of Approval of 27 New Drug Applications and 58...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-23

... oral pressurized metered-dose inhaler that contained chlorofluorocarbons (CFCs) as a propellant. CFCs may no longer be used as a propellant for any albuterol metered-dose inhalers. (See 70 FR 17168, April...

78 FR 43210 - Bracco Diagnostics et al.; Withdrawal of Approval of 52 New Drug Applications and 77 Abbreviated...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-19

... pressurized metered-dose inhaler that contained chlorofluorocarbons (CFCs) as a propellant. CFCs may no longer be used as a propellant for any albuterol metered-dose inhalers (see 70 FR 17168, April 4, 2005...

ALTERNATIVE FORMULATIONS TO REDUCE CFC USE IN U.S. EXEMPTED AND EXCLUSED AEROSOL PRODUCTS

EPA Science Inventory

The report examines products exempted and excluded from those affected by the 1978 ban on the use of chlorofluorocarbons (CFCs) as aerosol propellants, the present consumption of CFCs still utilized for these products in the U.S., and alternative formulations which may be used to...

ALTERNATIVE FORMULATIONS TO REDUCE CFC USE IN U.S. EXEMPTED AND EXCLUDED AEROSOL PRODUCTS

EPA Science Inventory

The report examines products exempted and excluded from those affected by the 1978 ban on the use of chlorofluorocarbons (CFCs) as aerosol propellants, the present consumption of CFCs still utilized for these products in the U.S., and alternative formulations which may be used to...

Sinclair Stockpiles CFCs for Future Use.

ERIC Educational Resources Information Center

George, Stephen C.

1996-01-01

A Dayton (Ohio) community college's 21 buildings were cooled by a network of 5 chillers, all of which used soon-to-be-banned chlorofluorocarbons (CFCs). A reclamation program provides the college with reusable refrigerant and eliminates chiller replacement costs. Refrigerant from three of the old units is stockpiled for use in the two other…

Investigations of the environmental acceptability of fluorocarbon alternatives to chlorofluorocarbons.

PubMed Central

McFarland, M

1992-01-01

Chlorofluorocarbons (CFCs) are currently used in systems for preservation of perishable foods and medical supplies, increasing worker productivity and consumer comfort, conserving energy and increasing product reliability. As use of CFCs is phased out due to concerns of ozone depletion, a variety of new chemicals and technologies will be needed to serve these needs. In choosing alternatives, industry must balance concerns over safety and environmental acceptability and still meet the preformance characteristics of the current technology, the only viable alternatives meeting the safety, performance, and environmental requirements for the remaining 40% of demand are fluorocarbons, hydrochlorofluorocarbons (HCFs), and hydrofluorocarbons (HFCs). HCFCs and HFCs possess many of the desirable properties of the CFCs, but because of the, hydrogen, they results in shorter atmospheric lifetimes compared to CFCs and reduces their potential to contribute to stratospheric ozone depletion or global warming; HFCs do not contain chlorine and have no potential to destroy ozone. This paper provides an overview of challenges faced by industry, regulators, and society in general in continuing to meet societal needs and consumer demands while reducing risk to the enviroment without compromising consumer or worker safety. PMID:11607257

Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2015-12-01

Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

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 amount of stratospheric halogenated gases during 1970-2012. Furthermore, a new theoretical calculation on the greenhouse effect of halogenated gases shows that they (mainly CFCs) could alone result in the global surface temperature rise of 0.6°C in 1970-2002. These results provide solid evidence that recent global warming was indeed caused by the greenhouse effect of anthropogenic halogenated gases. Thus, a slow reversal of global temperature to the 1950 value is predicted for coming 5 7 decades. It is also expected that the global sea level will continue to rise in coming 1 2 decades until the effect of the global temperature recovery dominates over that of the polar O3 hole recovery; after that, both will drop concurrently. All the observed, analytical and theoretical results presented lead to a convincing conclusion that both the CRE mechanism and the CFC-warming mechanism not only provide new fundamental understandings of the O3 hole and global climate change but have superior predictive capabilities, compared with the conventional models.

Mario Molina, Chlorofluorocarbons (CFCs), and Ozone Depletion

Science.gov Websites

Solomon, Chemical Heritage Foundation (CHF) Resources with Additional Information Additional information on Prize-winning Research, Massachusetts Institute of Technology (MIT) Interview with Mario J. Molina

TECHNOLOGIES FOR CFC/HALON DESTRUCTION

EPA Science Inventory

The report presents an overview of the current status of possible technologies used to destroy chlorofluorocarbons (CFCs) and halons chemicals implicated in the destruction of the stratospheric ozone layer. The Montreal Protocol an international treaty to control the production a...

EXPERIMENTAL INVESTIGATION OF PIC FORMATION DURING CFC INCINERATION

EPA Science Inventory

The report gives results of experiments to assess: (1) the effect of residual copper retained in an incineration facility on polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) formation during incineration of non-copper-containing chlorofluorocarbons (CFCs); and (2) th...

Comment on "Cosmic-ray-driven reaction and greenhouse effect of halogenated molecules: Culprits for atmospheric ozone depletion and global climate change"

NASA Astrophysics Data System (ADS)

Müller, Rolf; Grooß, Jens-Uwe

2014-04-01

Lu's "cosmic-ray-driven electron-induced reaction (CRE) theory" is based on the assumption that the CRE reaction of halogenated molecules (e.g., chlorofluorocarbons (CFCs), HCl, ClONO2) adsorbed or trapped in polar stratospheric clouds in the winter polar stratosphere is the key step in forming photoactive halogen species that are the cause of the springtime ozone hole. This theory has been extended to a warming theory of halogenated molecules for climate change. In this comment, we discuss the chemical and physical foundations of these theories and the conclusions derived from the theories. First, it is unclear whether the loss rates of halogenated molecules induced by dissociative electron attachment (DEA) observed in the laboratory can also be interpreted as atmospheric loss rates, but even if this were the case, the impact of DEA-induced reactions on polar chlorine activation and ozone loss in the stratosphere is limited. Second, we falsify several conclusions that are reported on the basis of the CRE theory: There is no polar ozone loss in darkness, there is no apparent 11-year periodicity in polar total ozone measurements, the age of air in the polar lower stratosphere is much older than 1-2 years, and the reported detection of a pronounced recovery (by about 20-25%) in Antarctic total ozone measurements by the year 2010 is in error. There are also conclusions about the future development of sea ice and global sea level which are fundamentally flawed because Archimedes' principle is neglected. Many elements of the CRE theory are based solely on correlations between certain datasets which are no substitute for providing physical and chemical mechanisms causing a particular behavior noticeable in observations. In summary, the CRE theory cannot be considered as an independent, alternative mechanism for polar stratospheric ozone loss and the conclusions on recent and future surface temperature and global sea level change do not have a physical basis.

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 Compound Problem

ERIC Educational Resources Information Center

Peffley, Nicole

2018-01-01

This inquiry-based lesson gets students moving to simulate chemical reactions in a way that allows them to visualize, understand, and retain information about chemical reactions in the stratosphere. Students then look at scientific data and conduct research to understand trends in the data and the impact of chlorofluorocarbons (CFCs). These…

Report on concentrations, lifetimes, and trends of CFCs, halons, and related species

NASA Technical Reports Server (NTRS)

Kaye, J. A. (Editor); Penkett, S. A. (Editor); Ormond, F. M. (Editor); Fraser, P.; Fisher, D.; Bloomfield, P.; Sander, S. P.; Ko, M. K. W.

1994-01-01

The atmospheric lifetimes of molecules containing chlorine and bromine are the dominant parameters influencing their ability to promote enhanced ozone destruction in the stratosphere. The purpose of this report is to assess the present state of knowledge of the lifetimes of halocarbons using two complementary approaches. First, a time series of measurements of gas concentrations is used together with information on their emissions histories and a computational model of atmospheric circulation and chemistry to infer lifetimes through a mass balance approach. Second, an atmospheric chemical-dynamical model is used with detailed information on the chemistry and spectroscopy of the molecules of interest to calculate lifetimes. The lifetimes determined by these two methods are then compared. Attention is focused most closely on fully halogenated chlorine- and bromine-containing molecules, primarily the chlorofluorocarbons, and the halons, because of their ability to deliver chlorine and bromine to the stratosphere. Some attention will be given to those molecules containing hydrogen, which are subject to removal in the troposphere primarily by reaction with OH and by other processes.

The Hole in the Ozone Layer.

ERIC Educational Resources Information Center

Hamers, Jeanne S.; Jacob, Anthony T.

This document contains information on the hole in the ozone layer. Topics discussed include properties of ozone, ozone in the atmosphere, chlorofluorocarbons, stratospheric ozone depletion, effects of ozone depletion on life, regulation of substances that deplete the ozone layer, alternatives to CFCs and Halons, and the future of the ozone layer.…

HEAT TRANSFER EVALUATION OF HFC-236EA AND CFC-114 IN CONDENSATION AND EVAPORATION

EPA Science Inventory

The report gives results of a heat transfer evaluation of the refrigerants hexafluoropropane (HFC-236ea) and 1,1,2,2-dichloro-tetrafluoroethane (CFC-114). (NOTE: With the mandatory phase-out of chlorofluorocarbons (CFCs), as dictated by the Montreal Protocol and Clean Air Act Ame...

EPA'S RESEARCH PROJECTS RELATING TO THE DUAL-CIRCUIT AND LORENZ REFRIGERATOR/FREEZERS

EPA Science Inventory

The paper discusses EPA research projects relating to the dual-circuit and Lorenz refrigerator/freezers (RFs). EPA is interested in not only phasing out chlorofluorocarbons (CFCs) in RFs, but doing so in a way that will maximize energy efficiency and minimize subsequent impacts o...

Mesoporous Fluorinated Metal-Organic Frameworks with Exceptional Adsorption of Fluorocarbons and CFCs

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

Chen, Teng-Hao; Popov, Ilya; Kaveevivitchai, Watchareeya

2016-02-08

Two mesoporous fluorinated metal–organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate- and tetrazolate-based ligands. The tetrazolate-based framework MOFF-5 has an accessible surface area of 2445 m 2g -1, the highest among fluorinated MOFs. Crystals of MOFF-5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)—the latter two being ozone-depleting substances and potent greenhouse species—with weight capacities of up to 225%. The material exhibits an apparent preference for the adsorption of non-spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride.

Ozone perturbations by enhanced levels of CFCs, N2O, and CH4 A two-dimensional diabatic circulation study including uncertainty estimates

NASA Technical Reports Server (NTRS)

Isaksen, I. S. A.; Stordal, F.

1986-01-01

Observations made over the last few years suggest that the tropospheric concentrations of N2O, CH4, and O3 are increasing. Increases in the concentration of chlorofluorocarbons (CFCs) have been observed for some time. The present study is concerned with combined scenarios of future releases of N2O, CH4, and CFCs, which can affect the height profiles of ozone, while changes in latitudinal gradients of ozone may also be expected. Ozone perturbation calculations performed in the two-dimensional transport-chemistry model described by Stordal et al. (1985) are also presented, and the effects of increased levels of CFCs, N2O, and CH4 are examined. It is found that CH4 may be the most important ozone-perturbing trace species in connection with future tropospheric climatic impacts. A substantial increase in the tropospheric abundancy of CH4 could lead to large future ozone enhancements throughout the troposphere and lower stratosphere at middle and low latitudes.

Ambient mixing ratios of atmospheric halogenated compounds at five background stations in China

NASA Astrophysics Data System (ADS)

Zhang, Gen; Yao, Bo; Vollmer, Martin K.; Montzka, Stephen A.; Mühle, Jens; Weiss, Ray F.; O'Doherty, Simon; Li, Yi; Fang, Shuangxi; Reimann, Stefan

2017-07-01

High precision measurements of three chlorofluorocarbons (CFCs), three hydrochlorofluorocarbons (HCFCs), six hydrofluorocarbons (HFCs), three perfluorocarbons (PFCs), and sulfur hexafluoride (SF6) were made at five Chinese background stations from January 2011 to December 2012. Their station means in the background air were 239.5 ± 0.69 parts-per-trillion dry-air mole fraction mixing ratios (ppt) for CFC-11, 536.5 ± 1.49 ppt for CFC-12, 74.66 ± 0.09 ppt for CFC-113, 232.1 ± 4.77 ppt for HCFC-22, 23.78 ± 0.29 ppt for HCFC-141b, 22.92 ± 0.42 ppt for HCFC-142b, 11.75 ± 0.43 ppt for HFC-125, 71.32 ± 1.35 ppt for HFC-134a, 13.62 ± 0.43 ppt for HFC-143a, 9.10 ± 1.26 ppt for HFC-152a, 25.45 ± 0.1 ppt for HFC-23, 7.28 ± 0.48 ppt for HFC-32, 4.32 ± 0.03 ppt for PFC-116, 0.63 ± 0.04 ppt for PFC-218, 1.36 ± 0.01 ppt for PFC-318, and 7.67 ± 0.03 ppt for SF6, respectively, which were comparable with those measured at the two Northern Hemisphere (NH) AGAGE stations: Mace Head, Ireland (MHD) and Trinidad Head, California, USA (THD). Compared with our results for earlier years from in-situ measurement at SDZ, background-air mixing ratios of CFCs are now declining, while those for HCFCs, HFCs, PFCs, and SF6 are still increasing. The ratios of the number of sampling events in which measured mixing ratios were elevated above background (pollution events) relative to the total sample frequency (POL/SUM) for CFCs, HCFCs, and HFCs were found to be station dependent, generally LAN > SDZ > LFS > XGL > WLG. The enhancement (△, polluted mixing ratios minus background mixing ratios) generally show distinct patterns, with HCFCs (40.7-175.4 ppt) > HFCs (15.8-66.3 ppt)> CFCs (15.8-33.8 ppt)> PFCs (0.1-0.9 ppt) at five stations, especially for HCFC-22 ranging from 36.9 ppt to 138.2 ppt. Combining with the molecular weights, our findings imply biggest emissions of HCFCs in the regions around these Chinese sites compared to HFCs and CFCs, while the smallest of PFCs, consistent with CFCs being phased out and replaced with HCFCs in China. In addition, relative emission strengths (emission was expressed by mole fractions) of these halocarbons in China were inferred as HCFC-22 > HCFC-141b > HFC-134a > HCFC-142b for the Yangtze River Delta (YRD) and as HCFC-22 > HCFC-142b > HCFC-141b ≈ HFC-134a in the North China Plain (NCP).

What would have happened to the ozone layer if chlorofluorocarbons (CFCs) had not been regulated?

NASA Astrophysics Data System (ADS)

Newman, P. A.; Oman, L. D.; Douglass, A. R.; Fleming, E. L.; Frith, S. M.; Hurwitz, M. M.; Kawa, S. R.; Jackman, C. H.; Krotkov, N. A.; Nash, E. R.; Nielsen, J. E.; Pawson, S.; Stolarski, R. S.; Velders, G. J.

2008-12-01

Ozone depletion by chlorofluorocarbons (CFCs) was first proposed by Molina and Rowland in their 1974 Nature paper. Since that time, the scientific connection between ozone losses and CFCs and other ozone depleting substances (ODSs) has been firmly established with laboratory measurements, atmospheric observations, and modeling research. The nations of the world implemented the Montreal Protocol (and amendments) which stopped ODS production in 1992. In this presentation we use a fully coupled radiation- chemical-dynamical model to simulate a future world where ODSs were never regulated and ODS production grew at an annual rate of 3%. In this "world avoided" simulation, 17% of the globally average column ozone is destroyed by 2020, and 67% is destroyed by 2065 in comparison to 1980. Large ozone depletions in the polar region become year-round rather than just seasonal as is currently observed in the Antarctic ozone hole. Very large temperature decreases are observed in response to circulation changes and decreased shortwave radiation absorption by ozone. Ozone levels in the tropical lower stratosphere remain constant until about 2053 and then collapse to near zero by 2058 as a result of heterogeneous chemical processes (as currently observed in the Antarctic ozone hole). The tropical cooling that triggers the ozone collapse is caused by an increase of the tropical upwelling. In response to ozone changes, ultraviolet (UV) radiation increases, tripling the erythemal (sunburn) radiation in the northern summer mid-latitudes by 2065.

Influence of the meteorological parameters on CFCs and SF6 concentration in the air of Krakow, Poland

NASA Astrophysics Data System (ADS)

Bielewski, Jarosław; Najman, Joanna; Śliwka, Ireneusz; Bartyzel, Jakub; Rosiek, Janusz

2013-04-01

key words: gas chromatography, trace gases, CFCs and SF6 measurements in urban area. Halogenated compounds (chlorofluorocarbons-CFCs), both natural and industrial, so-called freons, currently exist as trace gases in the entire human environment. The CFCs cause ozone depletion in the stratosphere. Moreover CFCs and SF6 take part in intensification of the greenhouse effect. The decisions of the Vienna Convention (1985) and of the Montreal Protocol (1987) limited the world production level of CFCs in the year 1989 at least 35% after 2004, 90% after 2015 and total reduction after year 2030. On account of international agreements, the measurements of CFCs and SF6 in air were started. Measurement "clean" stations were situated at places outside of urban areas influence and gathered on world program - AGAGE (Advanced Global Atmospheric Gases Experiment). One of these stations is Mace Head (Ireland, 53o N, 10o W), which participates in AGAGE since 1987 [1] and in European InGOS (Integrated non-CO2 Greenhouse gas Observing System) program since 2011. Similar research is also conducted in Central Europe, in urban area of Krakow (Poland, 50o N, 19o E) since 1997. The work discusses results from 15 years of concentration measurements (in the years 1997-2012) of selected halocarbons and SF6 in Krakow. To obtain concentrations of measured compounds the mathematical procedure has been used, where concentrations were calculated using a five points Lagrange's interpolation method. Using temporary measurement data were determined daily arithmetic means and their standard deviations. Based on these data, efficiency of Montreal Protocol legislation, implemented in Poland (The Journal of Laws No. 52) could be assessed [2]. Additionally cut-off filtration method was used to estimate trend of the base line of individual air pollutant. Rejected exceedances of base lines were corelated with meteorological characteristics of Krakow region to evaluate possible sources of pollution. The authors wish to acknowledge Prof. R. Weiss from Scripts Oceanography Institute (CA, USA) for preparing of the CFC's primary standard (SIO1993) and Dr M. Maiss from Max-Planck Institute (Germany) for SF6 calibration. Autors also thanks Prof. S. O'Doherty from University of Bristol (England) and Prof K. Rozanski from AGH University of Krakow (Poland) for calibration of the CFC's standard (SIO2005). The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) in the InGOS project under grant agreement n° 284274. The project is financed by the Polish National Science Center on the basis of Decision No. DEC-2011/01/N/ST10/07621. References: [1] Prinn R.G. et al., A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE. J.Geophys.Res. 105(D14), pp 17751 - 17792, 2000; [2] Śliwka I., et al., Long-Term Measurements of CFCs and SF6 Concentration in Air, Polish J. of Environ. Stud. Vol. 19, No. 4, 811-815, 2010;

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

Jordan, A.; Harnisch, J.; Borchers, R.

Previous investigations reported on the volcanic production of halocarbons including chlorofluorocarbons (CFCs). It has been suggested that this natural source could account for a significant atmospheric CFC background concentration, but no quantitative assessment of its source strength has yet been presented. The synthetic mechanism for their volcanic formation has neither been clarified. Fumarole and lava gas samples from four volcanoes (Kuju, Satsuma Iwojima, Mt. Etna, Vulcano) have been studied using gas chromatography/ion trap-mass spectrometry. More than 300 organic substances were detected, among which 5 fluorinated, 100 chlorinated, 25 brominated, and 4 iodinated compounds have been identified. The most abundant organohalogenmore » species were chlorinated methanes, unsaturated C{sub 2}-chlorohydrocarbons, and chlorobenzene, suggesting a synthetic course that includes the thermolytic formation of acetylene from hydrothermal methane, condensation reactions, and synchronous catalytic halogenation in the presence of highly activated surfaces of cooling magma or juvenile ash. The only CFC compound found was CFCl{sub 3} (CFC-11), which was detected in some samples at concentrations of up to 1 ppbv. A conservative estimate of the upper limit of global CFC emissions by volcanoes clearly shows that this source is negligible as compared to the atmospheric burden by anthropogenic activities.« less

78 FR 30830 - Promulgation of State Implementation Plan Revisions; Infrastructure Requirements for the 1997 and...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-23

... contact information unless you provide it in the body of your comment. If you send an email comment... information in the body of your comment and with any disk or CD-ROM you submit. If EPA cannot read your... (VOCs), chlorofluorocarbons (CFCs), smoke and odors. A summary of the regulations which the State...

Thomas Midgley, Jr., and the Development of New Substances: A Case Study for Chemical Educators

ERIC Educational Resources Information Center

Viana, Hélio Elael Bonini; Porto, Paulo Alves

2013-01-01

This paper presents a history of chemistry case study focusing on selected aspects of the work of American engineer Thomas Midgley, Jr. (1889-1944): the development of tetraethyl lead as an antiknock gasoline additive and of chlorofluorocarbons (CFCs) as fluids for refrigeration devices. One general aim of this case study is to display the complex…

What Would Have Happened to the Ozone Layer if Chlorofluorocarbons (CFCs) had not been Regulated?

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Oman, L. D.; Douglass, A. R.; Fleming, E. L.; Frith, S. M.; Hurwitz, M. M.; Kawa, S. R.; Jackman, C. H.; Krotkov, N. A.; Nash, E. R.;

76 FR 28707 - Approval and Promulgation of State Implementation Plan Revisions; Infrastructure Requirements for...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-18

... provide it in the body of your comment. If you send an e-mail comment directly to EPA, without going... body of your comment and with any disk or CD-ROM you submit. If EPA cannot read your comment due to...), chlorofluorocarbons (CFCs), smoke and odors. A summary of the regulations is found below under section 110(a)(2)(C). b...

Environmental Security: What Environmental Issues Impact Regional Stability and Affect United States Foreign Policy with Mexico?

DTIC Science & Technology

1997-03-01

extraregional sponsor of Alianza para el Desarrollo Sostenible (Sustainable Development Alliance - ALIDES), along with United States and Canada. ALIDES is...more stable the government the better the country will be able to solve its environmental problems. 42 Glossary ALIDES Alianza para el Desarrollo ... Sostenible (Sustainable Development Alliance) C Centigrade CFCs Chlorofluorocarbons BECC Border Environment Cooperation Commission BNC Binational

A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

NASA Astrophysics Data System (ADS)

Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

Residence times and age distributions of spring waters at the Semmering catchment area, Eastern Austria, as inferred from tritium, CFCs and stable isotopes.

PubMed

Han, Liangfeng; Hacker, Peter; Gröning, Manfred

2007-03-01

The groundwater system in the mountainous area of Semmering, Austria, was studied by environmental tracers in several karst springs. The tracers used included stable isotopes ((18)O, (2)H), tritium ((3)H) and chlorofluorocarbons (CFCs). The tracers provided valuable information in regard to (1) the mean altitude of the spring catchment areas; (2) the residence time and age distribution of the spring waters; and (3) the interconnection of the springs to a sinkhole. The combination of the stable isotopic data and the topography/geology provided the estimates of the mean altitudes of the catchment areas. Based on the stable isotopic data the recharge temperature of the spring waters was estimated. The smoothing of precipitation's isotopic signal in spring discharge provided information on the minimum transit time of the spring waters. Due to short observation time, (3)H data alone cannot be used for describing the mean residence time of the karst waters. CFCs, though useful in recognizing the co-existence of young (post-1993) water with old (CFC-free) water, could not be used to resolve age distribution models. It is shown in this article, however, that the combined use of tritium and CFCs can provide a better assessment of models to account for different groundwater age distributions. In Appendix A, a simplified method for collecting groundwater samples for the analysis of CFCs is described. The method provides a real facilitation for fieldwork. Test data are given for this sampling method in regard to potential contamination by atmospheric CFCs.

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.

Mineral resource of the month: fluorspar

USGS Publications Warehouse

,

2010-01-01

The article features the industrial mineral fluorspar, used in the manufacture of fluorochemicals, aluminum and steel. It defines fluorspar as crude or beneficiated material, mined or milled for the non-metallic mineral fluorite or calcium fluoride. Applications of acid-grade fluorspar in the U.S. are presented, including production of hydrofluoric acid for chemical production of refrigerants such as chlorofluorocarbons or CFCs. World demand for fluorspar decreased with the CFC ban in the 1990s, but recovered with the use of hydrofluorocarbons or HFCs.

Early trends in the global tropospheric abundance of hydrochlorofluorocarbon-141b and 142b

NASA Astrophysics Data System (ADS)

Montzka, S. A.; Myers, R. C.; Butler, J. H.; Elkins, J. W.

1994-11-01

Hydrochlorofluorocarbons (HCFCs) are rapidly replacing chlorofluorocarbons (CFCs) as foam-blowing agents, solvents, and refrigerants. These substitutes, however, still contain chlorine and have the potential to deplete stratospheric ozone. Although the ozone destruction capacity of HCFCs is believed to be significantly less than that for CFCs, concern over unrestricted chlorine input to the atmosphere from HCFC use has prompted proposals for future limits on production. Here we report the first global time-series for mixing ratios of HCFC-141b (1,1-dichloro-1-fluoroethane) and HCFC-142b (1-chloro-1,1-difluoroethane) in air collected at seven remote sampling stations. Global mean mixing ratios in mid-1993 were 0.7 parts per 1012 (ppt) for HCFC-141b and 4.3 ppt for HCFC-142b. The global atmospheric abundance of HCFC-141b increased by 0.9 ppt, or a factor of ˜3, in 1993. Global abundance of HCFC-142b increased by 1.1 ppt yr-1 during 1992-1993. The results suggest that HCFCs are currently used extensively for replacing CFCs in selected applications. Furthermore, measured levels are significantly higher than expected based on available emission estimates and consumption predictions.

The Importance of the Montreal Protocol in Protecting the Earth's Hydroclimate

NASA Astrophysics Data System (ADS)

Seager, R.; Wu, Y.; Polvani, L. M.

2012-12-01

The 1987 Montreal Protocol regulating emissions of ozone depleting chlorofluorocarbons (CFCs) was motivated primarily by the harm to human health and ecosystems arising from increased exposure to ultraviolet-B (UV-B) radiation associated with depletion from the ozone layer. It is now known that the Montreal Protocol has reduced global warming since CFCs are greenhouse gases (GHGs). In this paper we show that the Montreal Protocol also significantly protects the Earth's hydroclimate, even though this was also not a motivating factor in the decision-making that led to the Protocol. General Circulation Model (GCM) results show that in the coming decade (2020-29), under the 'World Avoided' scenario of no regulations on CFC emissions, the subtropical dry zones would in general get drier, and the middle and high latitude regions wetter. This change is similar, in both pattern and magnitude, to that in the coming decade caused by projected increases in carbon dioxide concentrations. This implies that because of the Montreal Protocol, and the ozone depletion and global warming associated with CFCs thus avoided, the hydrological cycle changes in the coming decade will be significantly less than what they otherwise would have been.

Linkages Between Ozone-depleting Substances, Tropospheric Oxidation and Aerosols

NASA Technical Reports Server (NTRS)

Voulgarakis, A.; Shindell, D. T.; Faluvegi, G.

2013-01-01

Coupling between the stratosphere and the troposphere allows changes in stratospheric ozone abundances to affect tropospheric chemistry. Large-scale effects from such changes on chemically produced tropospheric aerosols have not been systematically examined in past studies. We use a composition-climate model to investigate potential past and future impacts of changes in stratospheric ozone depleting substances (ODS) on tropospheric oxidants and sulfate aerosols. In most experiments, we find significant responses in tropospheric photolysis and oxidants, with small but significant effects on methane radiative forcing. The response of sulfate aerosols is sizeable when examining the effect of increasing future nitrous oxide (N2O) emissions. We also find that without the regulation of chlorofluorocarbons (CFCs) through the Montreal Protocol, sulfate aerosols could have increased by 2050 by a comparable amount to the decreases predicted due to relatively stringent sulfur emissions controls. The individual historical radiative forcings of CFCs and N2O through their indirect effects on methane (-22.6mW/sq. m for CFCs and -6.7mW/sq. m for N2O) and sulfate aerosols (-3.0mW/sq. m for CFCs and +6.5mW/sq. m for N2O when considering the direct aerosol effect) discussed here are non-negligible when compared to known historical ODS forcing. Our results stress the importance of accounting for stratosphere-troposphere, gas-aerosol and composition-climate interactions when investigating the effects of changing emissions on atmospheric composition and climate.

Distribution and ventilation of water masses in the western Ross Sea inferred from CFC measurements

NASA Astrophysics Data System (ADS)

Rivaro, Paola; Ianni, Carmela; Magi, Emanuele; Massolo, Serena; Budillon, Giorgio; Smethie, William M.

2015-03-01

During the CLIMA Project (R.V. Italica cruise PNRA XVI, January-February 2001), hydrographic and chlorofluorocarbons (CFCs) observations were obtained, particularly in the western Ross Sea. Their distribution demonstrated water mass structure and ventilation processes in the investigated areas. In the surface waters (AASW) the CFC saturation levels varied spatially: CFCs were undersaturated in all the areas (range from 80 to 90%), with the exception of few stations sampled near Ross Island. In particular, the Terra Nova Bay polynya, where high salinity shelf water (HSSW) is produced, was a low-saturated surface area (74%) with respect to CFCs. Throughout most of the shelf area, the presence of modified circumpolar deep water (MCDW) was reflected in a mid-depth CFC concentration minima. Beneath the MCDW, CFC concentrations generally increased in the shelf waters towards the seafloor. We estimated that the corresponding CFCs saturation level in the source water region for HSSW was about 68-70%. Waters with high CFC concentrations were detected in the western Ross Sea on the down slope side of the Drygalski Trough, indicating that AABW was being supplied to the deep Antarctic Basin. Estimates of ventilation ages depend strongly on the saturation levels. We calculated ventilation ages using the saturation level calibrated tracer ratio, CFC11/CFC12. We deduced a mean residence time of the shelf waters of about 6-7 years between the western Ross Sea source and the shelf break.

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 pesticide methyl bromide (CH3Br), for example, was applied primarily in southern Europe to protect vegetable and strawberry plantations. Its production was banned by the Montreal Protocol which is reflected by a strong reduction in emissions between 2003 and 2008 as seen from Jungfraujoch. A contrasting example is the cooling agent HFC-125 belonging to the second generation of replacement compounds not regulated under the Montreal Protocol. During the same period, HFC-125 exhibited a marked increase with sources more homogeneously spread over Europe than those of CH3Br. For a more quantitative analysis for the years 2007-2009, we applied the Lagrangian Particle Dispersion Model FLEXPART using meteorological input data of the IFS model of ECMWF at 0.2° x 0.2° resolution, together with a new source inversion method based on sequential Kalman filtering. Different from other approaches the method is essentially independent of an a-priori and adjusts both the emission field and the trace gas background levels in an iterative fashion. In this study, we will contrast results of the trajectory statistics method with the more advanced source inversion, address uncertainties in the methods, and show the evolution of European emissions of a selection of compounds in comparison to official numbers reported by the individual countries to the Montreal and Kyoto protocols, respectively.

Early trends in the global tropospheric abundance of hydrochlorofluorocarbon-141b and 142b

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

Montzka, S.A.; Myers, R.C.; Butler, J.H.

1994-11-15

Hydrochlorofluorocarbons (HCFCs) are rapidly replacing chlorofluorocarbons (CFCs) as foam-blowing agents, solvents, and refrigerants. These substitutes, however, still contain chlorine and have the potential to deplete stratospheric ozone. Although the ozone destruction capacity of HCFCs is believed to be significantly less than that for CFCs, concern over unrestricted chlorine input to the atmosphere from HCFC use has prompted proposals for future limits on production. The authors report the first global time-series for mixing ratios of HCFC-141b (1,1-dichloro-1-fluoroethane) and HCFC-142b (1-chloro-1,1-difluoroethane) in air collected at seven remote sampling stations. Global mean mixing ratios in mid-1993 were 0.7 parts per 10{sup 12} (ppt)more » for HCFC-141b and 4.3 ppt for HCFC-142b. The global atmospheric abundance of HCFC-141b increased by 0.9 ppt, or a factor of {approximately} 3, in 1993. Global abundance of HCFC-142b increased by 1.1 ppt yr{sup {minus}1} during 1992-1993. The results suggest that HCFCs are currently used extensively for replacing CFCs in selected applications. Furthermore, measured levels are significantly higher than expected based on available emission estimates and consumption predictions. 24 refs., 4 figs.« less

Volatile organic compounds in the unsaturated zone from radioactive wastes

USGS Publications Warehouse

Baker, Ronald J.; Andraski, Brian J.; Stonestrom, David A.; Luo, Wentai

2012-01-01

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0–2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m-2 yr-1. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.

STUDIES OF HALOGENATED HYDROCARBONS. PART 1 - STABILITY OF FLUOROCARBONS IN AIR OVER HOPCALITE CATALYST OR STAINLESS STEEL

DTIC Science & Technology

A study was made of the catalytic decomposition of a number of fluorine-containing halogenated hydrocarbons in air, using Hopcalite catalyst in a... Hopcalite catalyst had no significant effect on the rate of decomposition of the chlorofluorocarbons. Sulfur hexafluoride in air was stable over Hopcalite ...as those of nuclear submarines. Where they are needed, as in refrigeration systems, it is recommended that R-114, R-14, or R-12 be used since they show the greatest resistance to Hopcalite -catalyzed decomposition.

The effect of environmental initiatives on NASA specifications and standards activities

NASA Technical Reports Server (NTRS)

Griffin, Dennis; Webb, David; Cook, Beth

1995-01-01

The NASA Operational Environment Team (NOET) has conducted a survey of NASA centers specifications and standards that require the use of Ozone Depleting Substances (ODS's) (Chlorofluorocarbons (CFCs), Halons, and chlorinated solvents). The results of this survey are presented here, along with a pathfinder approach utilized at Marshall Space Flight Center (MSFC) to eliminate the use of ODS's in targeted specifications and standards. Presented here are the lessons learned from a pathfinder effort to replace CFC-113 in a significant MSFC specification for cleaning and cleanliness verification methods for oxygen, fuel and pneumatic service, including Shuttle propulsion elements.

Stratospheric ozone, global warming, and the principle of unintended consequences--an ongoing science and policy success story.

PubMed

Andersen, Stephen O; Halberstadt, Marcel L; Borgford-Parnell, Nathan

2013-06-01

In 1974, Mario Molina and F. Sherwood Rowland warned that chlorofluorocarbons (CFCs) could destroy the stratospheric ozone layer that protects Earth from harmful ultraviolet radiation. In the decade after scientists documented the buildup and long lifetime of CFCs in the atmosphere; found the proof that CFCs chemically decomposed in the stratosphere and catalyzed the depletion of ozone; quantified the adverse effects; and motivated the public and policymakers to take action. In 1987, 24 nations plus the European Community signed the Montreal Protocol. Today, 25 years after the Montreal Protocol was agreed, every United Nations state is a party (universal ratification of 196 governments); all parties are in compliance with the stringent controls; 98% of almost 100 ozone-depleting chemicals have been phased out worldwide; and the stratospheric ozone layer is on its way to recovery by 2065. A growing coalition of nations supports using the Montreal Protocol to phase down hydrofluorocarbons, which are ozone safe but potent greenhouse gases. Without rigorous science and international consensus, emissions of CFCs and related ozone-depleting substances (ODSs) could have destroyed up to two-thirds of the ozone layer by 2065, increasing the risk of causing millions of cancer cases and the potential loss of half of global agricultural production. Furthermore, because most, ODSs are also greenhouse gases, CFCs and related ODSs could have had the effect of the equivalent of 24-76 gigatons per year of carbon dioxide. This critical review describes the history of the science of stratospheric ozone depletion, summarizes the evolution of control measures and compliance under the Montreal Protocol and national legislation, presents a review of six separate transformations over the last 100 years in refrigeration and air conditioning (A/C) technology, and illustrates government-industry cooperation in continually improving the environmental performance of motor vehicle A/C.

Stratospheric ozone, global warming, and the principle of unintended consequences-An ongoing science and policy success story.

PubMed

Andersen, Stephen O; Halberstadt, Marcel L; Borgford-Parnell, Nathan

2013-06-01

In 1974, Mario Molina and F. Sherwood Rowland warned that chlorofluorocarbons (CFCs) could destroy the stratospheric ozone layer that protects Earth from harmful ultraviolet radiation. In the decade after, scientists documented the buildup and long lifetime of CFCs in the atmosphere; found the proof that CFCs chemically decomposed in the stratosphere and catalyzed the depletion of ozone; quantified the adverse effects; and motivated the public and policymakers to take action. In 1987, 24 nations plus the European Community signed the Montreal Protocol. Today, 25 years after the Montreal Protocol was agreed, every United Nations state is a party (universal ratification of 196 governments); all parties are in compliance with the stringent controls; 98% of almost 100 ozone-depleting chemicals have been phased out worldwide; and the stratospheric ozone layer is on its way to recovery by 2065. A growing coalition of nations supports using the Montreal Protocol to phase down hydrofluorocarbons, which are ozone safe but potent greenhouse gases. Without rigorous science and international consensus, emissions of CFCs and related ozone-depleting substances (ODSs) could have destroyed up to two-thirds of the ozone layer by 2065, increasing the risk of causing millions of cancer cases and the potential loss of half of global agricultural production. Furthermore, because most ODSs are also greenhouse gases, CFCs and related ODSs could have had the effect of the equivalent of 24-76 gigatons per year of carbon dioxide. This critical review describes the history of the science of stratospheric ozone depletion, summarizes the evolution of control measures and compliance under the Montreal Protocol and national legislation, presents a review of six separate transformations over the last 100 years in refrigeration and air conditioning (A/C) technology, and illustrates government-industry cooperation in continually improving the environmental performance of motor vehicle A/C. [Box: see text].

Early work on the stratospheric ozone depletion-CFC issue

NASA Astrophysics Data System (ADS)

Molina, M.

2012-12-01

I became involved with the atmospheric chemistry of chlorofluorocarbons (CFCs) shortly after joining Sherry Rowland's research group at the University of California, Irvine, in 1973. CFCs had been detected in the troposphere by James Lovelock in 1971, and the question we set out to answer was the fate of these compounds of industrial origin in the environment, as well as possibly identifying any consequences of their accumulation in the atmosphere. After examining many potential sinks for these compounds we realized that because of their unusual stability the most likely destruction process was photolysis in the stratosphere. I carried out measurements of the absorption spectra of these compounds in the near ultraviolet; previous work involved only spectra in the far ultraviolet, not relevant for atmospheric chemistry. The results indicated that photolysis would take place in the upper stratosphere. I subsequently carried out calculations using one-dimensional atmospheric models to estimate their atmospheric residence times, which turned out to be many decades. We realized that the chlorine atoms generated by photolysis of the CFCs would participate in a catalytic chain reaction that would efficiently destroy ozone. Furthermore, we estimated that the amount of CFCs produced industrially was comparable to the amount of nitric oxide produced naturally in the stratosphere by the decomposition of nitrous oxide; work by Paul Crutzen and Harold Johnston had indicated that the abundance of ozone in the stratosphere was controlled by nitric oxide. We then formulated the hypothesis that the continued release of CFCs to the environment posed a threat to the stability of the ozone layer, and published our results in the journal Nature in 1974. The publication was noticed almost exclusively by the community of experts in stratospheric chemistry, and hence Sherry Rowland and I decided at that time that it was our responsibility to communicate this finding to society at large, and particularly to decision makers in government, while at the same time promoting additional scientific research to test the validity of our hypothesis.

Awareness of environmental issues and the acceptance of CFC-free inhalers.

PubMed

Goh, S Y; Arulanandam, S; Ho, C L; Zhang, L; Goh, D Y; Chew, F T; Lee, B W

1998-09-01

With the recent availability of a chlorofluorocarbon (CFC)-free metered dose inhaler (MDI) (Airomir), a patient survey was carried out to evaluate awareness of the role of CFCs in our environment and acceptance of this new inhaler. A questionnaire survey was conducted on parents and guardians of 201 children. Depending on respondents' preference, the interview was conducted in English (71%), Chinese (23%), Malay (5%) or Tamil (1%). A 'taste' test was also conducted on 103 of these children. Only 13% (26/201) of parents/guardians were aware that MDIs contained CFCs. Although 70% of children were in favour of the new taste of the CFC-free inhaler, the cost of the new inhaler was an important consideration for parents and guardians in their decision to switch to the new inhaler. The majority (93%) were willing to switch if its cost were equivalent to their current inhaler. This study has provided pertinent information with regard to acceptance of CFC-free inhalers which should be considered when making the inevitable switch to environmentally friendly inhalers.

The president speaks: prevention is best: lessons from protecting the ozone layer.

PubMed

Woodcock, Ashley

2012-12-01

The Montreal Protocol was signed 25 years ago. As a result, the irreversible destruction of the ozone layer was prevented. However, stratospheric ozone will not recover completely until 2060 and the consequent epidemic in skin cancer cases will persist until 2100. Many millions of patients with asthma and chronic obstructive pulmonary disease have safely switched from chlorofluorocarbon (CFC)-powered metered-dose inhalers (MDIs) to either hydrofluorocarbon (HFC) or DPIs. China will be the last country to phase out CFCs by 2016. HFCs are global warming gases which will be controlled in the near future. HFCs in MDIs may be phased out over the next 10-20 years.

EOS CHEM: A Mission to Study Ozone and Climate

NASA Technical Reports Server (NTRS)

Schoeberl, Mark

1998-01-01

The Earth's stratosphere contains the ozone layer, which shields us from the Sun@ harmful ultraviolet (UV) radiation. Ozone is destroyed through chemical reactions involving natural and man-made nitrogen, hydrogen, bromine, and chlorine compounds. The release of chlorofluoro-carbons CFCs) has caused a dramatic decrease in the protective stratospheric ozone layer during the last two decades. Detection of stratospheric ozone depletion led to regulation and phase-out of CFC production worldwide. As a result, man-made chlorine levels in the atmosphere are slowly beginning to decrease. CHEM will be able to determine whether the stratospheric ozone layer is now recovering, as predicted by scientific models.

Chemical quality of base flow in 18 selected streams in the upper Susquehanna River basin, New York

USGS Publications Warehouse

Hetcher, Kari K.; Miller, Todd S.; Komor, Steven C.

2004-01-01

Ground water from four production wells in the villages of Afton, Sidney, Unadilla, and Otego was analyzed for chlorofluorocarbons (CFCs) to indicate the approximate age of the water in these wells and the potential for induced infiltration of river water. The water at two of these wells is probably between 26 and 50 years old; the ages of water at the other two wells could not be reliably estimated because of CFC contamination from a nonatmospheric source. The two wells for which CFC analysis gave reliable results (Afton and Otego) probably do not induce infiltration of river water into the aquifer.

European emissions of halogenated greenhouse gases inferred from atmospheric measurements.

PubMed

Keller, Christoph A; Hill, Matthias; Vollmer, Martin K; Henne, Stephan; Brunner, Dominik; Reimann, Stefan; O'Doherty, Simon; Arduini, Jgor; Maione, Michela; Ferenczi, Zita; Haszpra, Laszlo; Manning, Alistair J; Peter, Thomas

2012-01-03

European emissions of nine representative halocarbons (CFC-11, CFC-12, Halon 1211, HCFC-141b, HCFC-142b, HCFC-22, HFC-125, HFC-134a, HFC-152a) are derived for the year 2009 by combining long-term observations in Switzerland, Italy, and Ireland with campaign measurements from Hungary. For the first time, halocarbon emissions over Eastern Europe are assessed by top-down methods, and these results are compared to Western European emissions. The employed inversion method builds on least-squares optimization linking atmospheric observations with calculations from the Lagrangian particle dispersion model FLEXPART. The aggregated halocarbon emissions over the study area are estimated at 125 (106-150) Tg of CO(2) equiv/y, of which the hydrofluorocarbons (HFCs) make up the most important fraction with 41% (31-52%). We find that chlorofluorocarbon (CFC) emissions from banks are still significant and account for 35% (27-43%) of total halocarbon emissions in Europe. The regional differences in per capita emissions are only small for the HFCs, while emissions of CFCs and hydrochlorofluorocarbons (HCFCs) tend to be higher in Western Europe compared to Eastern Europe. In total, the inferred per capita emissions are similar to estimates for China, but 3.5 (2.3-4.5) times lower than for the United States. Our study demonstrates the large benefits of adding a strategically well placed measurement site to the existing European observation network of halocarbons, as it extends the coverage of the inversion domain toward Eastern Europe and helps to better constrain the emissions over Central Europe.

Exploring Hydrofluorocarbons as Groundwater Age Tracers (Invited)

NASA Astrophysics Data System (ADS)

Haase, K. B.; Busenberg, E.; Plummer, L. N.; Casile, G.; Sanford, W. E.

2013-12-01

Groundwater dating tracers are an essential tool for analyzing hydrologic conditions in groundwater systems. Commonly used tracers for dating post-1940's groundwater include sulfur hexafluoride (SF6), chlorofluorocarbons (CFCs), 3H-3He, and other isotopic tracers (85Kr, δ2H and δ18O isotopes, etc.). Each tracer carries a corresponding set of advantages and limitations imposed by field, analytical, and interpretive methods. Increasing the number available tracers is appealing, particularly if they possess inert chemical properties and unique temporal emission histories from other tracers. Atmospherically derived halogenated trace gases continue to hold untapped potential for new tracers, as they are generally inert and their emission histories are well documented. SF5CF3, and CFC-13 were previously shown to have application as dating tracers, though their low mixing ratios and low solubility require large amounts of water to be degassed for their quantification. Two related groups of compounds, hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are hypothesized to be potential age tracers, having similar mixing ratios to the CFCs and relatively high solubility. However, these compounds yield gas chromatography electron capture detector (GC-ECD) responses that are 10-2 -10-5 less than CFC-12, making purge and trap or field stripping GC-ECD approaches impractical. Therefore, in order to use dissolved HCFCs and HFCs as age tracers, different approaches are needed. To solve this problem, we developed an analytical method that uses an atomic emission detector (GC-AED) in place of an ECD to detect fluorinated compounds. In contrast to the ECD, the AED is a universally sensitive, highly linear, elementally specific detector. The new GC-AED system is being used to measure chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a), and other fluorinated compounds in one liter water samples to study their potential as age dating tracers. HCFC-22 is a refrigerant introduced in the 1940's, with atmospheric mixing ratios increasing through the 1990s to the present value of ≈230 pptv. HFC-134a is typically is used as a chlorine-free replacement for CFC-12, finding use in air-condition systems and as an inert aerosol blowing agent, with a mixing ratio that has increased from <1 in 1994 to ≈75 pptv at present (2013). Their unique atmospheric histories and chemistry compared to CFCs makes these compounds interesting age tracer candidates, particularly in situations where multiple tracers enhance interpretive value. For instance, inclusion in lumped parameter mixing models and in situations where SF6 or the CFCs are present in elevated concentrations from non-atmospheric sources such that they cannot be used for dating purposes. Analysis of standards, air equilibrated water, and blanks suggests the GC-AED system is capable of detecting concentrations ≈200 fM (HCFC-22) and ≈100 fM (HFC-134a), corresponding to piston flow ages of 54 and 18 yr, respectively, with a typical uncertainty of ≈1 yr. Preliminary comparisons with CFC and SF6 analyses show general agreement between the techniques (within a few years), and ongoing intercomparison studies will be discussed.

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh.

PubMed

Horneman, A; Stute, M; Schlosser, P; Smethie, W; Santella, N; Ho, D T; Mailloux, B; Gorman, E; Zheng, Y; van Geen, A

2008-04-04

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.

Chlorofluorocarbons as tracers of groundwater transport processes in a shallow, silty sand aquifer

USGS Publications Warehouse

Cook, P.G.; Solomon, D.K.; Plummer, Niel; Busenberg, E.; Schiff, S.L.

1995-01-01

Detailed depth profiles of Chlorofluorocarbons CFC-11(CFCl3(, CFC-12 (CF2Cl2) and CFC-113 (C2F3Cl3) have been obtained from a well-characterized field site in central Ontario. Aquifer materials comprise predominantly silty sands, with a mean organic carbon content of 0.03%. Nearly one-dimensional flow exists at this site, and the vertical migration of a well-defined 3H peak has been tracked through time. Detailed vertical sampling has allowed CFC tracer velocities to be estimated to within 10%. Comparison with 3H profiles enables estimation of chlorofluorocarbon transport parameters. CFC-12 appears to be the most conservative of the CFCs measured. Sorption at this site is low (Kd < 0.03), and degradation does not appear to be important. CFC- 113 is retarded both with respect to CFC-12 and with respect to 3H (Kd = 0.09−0.14). CFC-11 appears to be degraded both in the highly organic unsaturated zone and below 3.5 m depth in the aquifer, where dissolved oxygen concentrations decrease to below 0.5 mg L−1. The half-life for CFC-11 degradation below 3.5 m depth is less than 2 years. While apparent CFC-12 ages match hydraulic ages to within 20% (up to 30 years), apparent CFC-11 and CFC-113 ages significantly overestimate hydraulic ages at our field site.

The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations

NASA Technical Reports Server (NTRS)

Brasseur, G.; Derudder, A.

1987-01-01

The response of the atmosphere to emissions of chlorofluorocarbons (CFCs) and other chlorocarbons, and to increasing concentrations of other radiatively active trace gases such as CO2, CH4, and N2O is calculated by a coupled chemical-radiative transport one-dimensional model. It is shown that significant reductions in the ozone concentration and in the temperature are expected in the upper stratosphere as a result of increasing concentrations of active chlorine produced by photodecomposition of the CFCs. The ozone content is expected to increase in the troposphere, as a consequence of increasing concentrations of methane and nitrogen oxides. Due to enhanced greenhouse effects, the Earth's surface should warm up by several degrees. The amplitude and even the sign of future changes in the ozone column are difficult to predict as they are strongly scenario-dependent. An early detection system to prevent noticeable ozone changes as a result of increasing concentrations of source gases should thus be based on a continuous monitoring of the ozone amount in the upper stratosphere rather than on measurements of the ozone column only. Measurements of NOx, Clx, and HOx are also required for unambiguous trend detection and interpretation.

Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons

DOE Data Explorer

Blasing, T. J.; Jones, Sonja

2012-02-01

Chlorofluorocarbons (CFCs) contain Carbon and some combination of Fluorine and Chlorine atoms. Hydrofluorocarbons (HFCs) contain Hydrogen, Fluorine, and Carbon (no chlorine). Hydrochlorofluorocarbons (HCFCs) contain Hydrogen, Chlorine, Fluorine, and Carbon atoms. Hydrobromofluorocarbons (HBFCs) contain Hydrogen, Bromine, Fluorine, and Carbon atoms. Perfluorocarbons contain Fluorine, Carbon, and Bromine atoms, and some contain Chlorine and/or Hydrogen atoms. These compounds are often designated by a combination of letters and numbers (e.g., CFC-11, HCFC-142b). In the latter example, the lower-case b refers to an isomer, which has no relationship to the chemical formula (C2H3F2Cl), but designates a particular structural arrangement of the atoms included. For example, HCFC-142b identifies the isomer in which all three hydrogen atoms are attached to the same carbon atom, and the structural formula is written as CH3CF2Cl. By contrast, HCFC-142 (without the b) refers to an arrangement in which one carbon atom is attached to two hydrogen atoms and one chlorine atom, while the other carbon atom is attached to the third hydrogen atom and two fluorine atoms. Hence, it has a different structural formula (CH2ClCHF2).

Biodegradation of Chlorofluorocarbons in a Groundwater Plume using Compound Specific Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Phillips, E.; Manna, J.; Horst, A.; Gilevska, T.; Sherwood Lollar, B.; Mack, E. E.; Seger, E.; Lutz, E. J.; Norcoss, S.; Morgan, S. E.; West, K. A.; Dworatzek, S.; Webb, J.

2017-12-01

Compound specific isotope analysis (CSIA) measures isotope ratios of organic hydrocarbons to monitor intrinsic bioremediation processes that can transform contaminants in field settings. The fraction of original contaminant remaining can be determined using the measured isotope ratio of the contaminant by an experimentally determined fractionation factor. In this study, two separate biotransformation experiments were performed in the Stable Isotope Laboratory at the University of Toronto using CSIA. In these two experiments, a mixed culture derived from a contaminated site was amended with trichlorotrifluoroethane (CFC-113), or trichlorofluoromethane (CFC-11), respectively. The concentrations and carbon isotope ratios of CFC-113, or CFC-11 were analyzed to calculate the fractionation factor for the transformation of each compound. Subsequently, groundwater samples from 9 wells at a historically contaminated site were collected and analyzed. The experimentally determined fractionation factors were then used to evaluate the extent of transformation that had occurred at the field site. In the laboratory studies, significant carbon isotope fractionation was observed for both CFC-113 and CFC-11 as biotransformation proceeded. This significant fractionation is beneficial when evaluating biotransformation at field sites as it can be clearly differentiated from the effects of other physical processes such as transport, or volatilization. Although there was significant variation in the carbon isotope values of CFC-113 between different well locations at the field site, these variations may be due to differences in source carbon isotope signatures. For CFC-11, much more significant isotopic variation was observed within the same well and between wells, showing trends consistent with in situ biotransformation. Results from this study demonstrate that CSIA can be successfully applied to evaluate the extent of transformation of chlorofluorocarbons (CFCs) at contaminated field sites, which has not been shown previously. This study also demonstrates that biotransformation may play a more significant role in the natural attenuation of CFCs than has previously been recognized.

Protecting the ozone layer.

PubMed

Munasinghe, M; King, K

1992-06-01

Stratospheric ozone layer depletion has been recognized as a problem by the Vienna Convention for the Protection of the Ozone Layer and the 1987 Montreal Protocol (MP). The ozone layer shields the earth from harmful ultraviolet radiation (UV-B), which is more pronounced at the poles and around the equator. Industrialized countries have contributed significantly to the problem by releasing chlorofluorocarbons (CFCs) and halons into the atmosphere. The effect of these chemicals, which were known for their inertness, nonflammability, and nontoxicity, was discovered in 1874. Action to deal with the effects of CFCs and halons was initiated in 1985 in a 49-nation UN meeting. 21 nations signed a protocol limiting ozone depleting substances (ODS): CFCs and halons. Schedules were set based on each country's use in 1986; the target phaseout was set for the year 2000. The MP restricts trade in ODSs and weights the impact of substances to reflect the extent of damage; i.e., halons are 10 times more damaging than CFCs. ODS requirements for developing countries were eased to accommodate scarce resources and the small fraction of ODS emissions. An Interim Multilateral Fund under the Montreal Protocol (IMFMP) was established to provide loans to finance the costs to developing countries in meeting global environmental requirements. The IMFMP is administered by the World Bank, the UN Environmental Program, and the UN Development Program. Financing is available to eligible countries who use .3 kg of ODS/person/year. Rapid phaseout in developed countries has occurred due to strong support from industry and a lower than expected cost. Although there are clear advantages to rapid phaseout, there were no incentives included in the MP for rapid phaseout. Some of the difficulties occur because the schedules set minimum targets at the lowest possible cost. Also, costs cannot be minimized by a country-specific and ODS-specific process. The ways to improve implementation in scheduling and incremental costs are indicated.

Volatile organic compounds and isoprene oxidation products at a temperate deciduous forest site

NASA Astrophysics Data System (ADS)

Helmig, Detlev; Greenberg, Jim; Guenther, Alex; Zimmerman, Pat; Geron, Chris

1998-09-01

Biogenic volatile organic compounds (BVOCs) and their role in atmospheric oxidant formation were investigated at a forest site near Oak Ridge, Tennessee, as part of the Nashville Southern Oxidants Study (SOS) in July 1995. Of 98 VOCs detected, a major fraction were anthropogenic VOCs such as chlorofluorocarbons (CFCs), alkanes, alkenes and aromatic compounds. Isoprene was the dominant BVOC during daytime. Primary products from BVOC oxidation were methylvinylketone, methacrolein and 3-methylfuran. Other compounds studied include the BVOCs α-pinene, camphene, β-pinene, p-cymene, limonene and cis-3-hexenyl acetate and a series of light alkanes, aromatic hydrocarbons and seven of the CFCs. The correlation of meteorological parameters, with the mixing ratios of these different compounds, reveals information on atmospheric oxidation processes and transport. Long-lived VOCs show very steady mixing ratio time series. Regionally and anthropogenically emitted VOCs display distinct diurnal cycles with a strong mixing ratio decrease in the morning from the breakup of the nocturnal boundary layer. Nighttime mixing ratio increases of CFCs and anthropogenic VOCs are suspected to derive from emissions within the Knoxville urban area into the shallow nocturnal boundary layer. In contrast, the time series of BVOCs and their oxidation products are determined by a combination of emission control, atmospheric oxidation and deposition, and boundary layer dynamics. Mixing ratio time series data for monoterpenes and cis-3-hexenyl acetate suggest a temporarily emission rate increase during and after heavy rain events. The isoprene oxidation products demonstrate differences in the oxidation pathways during night and day and in their dry and wet deposition rates.

Mechanistic insights aid the search for CFC substitutes: risk assessment of HCFC-123 as an example.

PubMed

Jarabek, A M; Fisher, J W; Rubenstein, R; Lipscomb, J C; Williams, R J; Vinegar, A; McDougal, J N

1994-06-01

An international consensus on the need to reduce the use of chlorofluorocarbons (CFCs) and other ozone-depleting gases such as the halons led to the adoptions of the 1987 Montreal Protocol and Title VI of the 1990 Clean Air Act Amendments, "Protecting Stratospheric Ozone." These agreements included major provisions for reducing and eventually phasing out production and use of CFCs and halons as well as advancing the development of replacement chemicals. Because of the ubiquitous use and benefits of CFCs and halons, an expeditious search for safe replacements to meet the legislative deadlines is of critical importance. Toxicity testing and health risk assessment programs were established to evaluate the health and environmental impact of these replacement chemicals. Development and implementation of these programs as well as the structural-activity relationships significant for the development of the replacement chemicals are described below. A dose-response evaluation for the health risk assessment of the replacement chemical HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane) is also presented to show an innovative use of physiologically based pharmacokinetic (PBPK) modeling. This is based on a parallelogram approach using data on the anesthetic gas halothane, a structural analog to HCFC-123. Halothane and HCFC-123 both form the same metabolite, trifluoroacetic acid (TFA), indicative of the same metabolic oxidative pathway attributed to hepatotoxicity. The parallelogram approach demonstrates the application of template model structures and shows how PBPK modeling, together with judicious experimental design, can be used to improve the accuracy of health risk assessment and to decrease the need for extensive laboratory animal testing.

An evaluation of alternative cleaning methods for removing an organic contaminant from a stainless steel part

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

Boyd, J.L.

1996-08-01

As of December 1995, the manufacture of Freon, along with many other chlorofluorocarbons (CFCs), was prohibited by the Clean Air Act of 1990 (CAA). The ban of CFC solvents has forced manufacturers across the country to search for alternative metal cleaning techniques. The objective of this study was to develop a thorough, scientific based approach for resolving one specific manufacturer`s problem of removing organic contamination from a stainless steel part. This objective was accomplished with an approach that involved: (1) defining the problem, (2) identifying the process constraints, (3) researching alternate cleaning methods, (4) researching applicable government regulations, (5) performingmore » a scientific evaluation and (6) drawing conclusions.« less

Dynamics of CFCs in northern temperate lakes and adjacent groundwater

USGS Publications Warehouse

Walker, John F.; Saad, David A.; Hunt, Randall J.

2007-01-01

Three dimictic lakes and one meromictic lake in and near the Trout Lake, Wisconsin, watershed were sampled to determine the variation of chlorofluorocarbon (CFC) concentrations within the lakes. The lakes were sampled during stratified conditions, during fall turnover, and during ice cover. The results demonstrate a considerable variation in CFC concentrations and corresponding atmospheric mixing ratios in the lakes sampled, both with depth and season within a given lake, and across different lakes. CFC profiles and observed degradation were not related to the groundwater inflow rate and hence are likely the result of in‐lake processes influenced by CFC degradation in the (lake) water column, CFC degradation in the lake‐bed sediments, and gas exchange rates and the duration of turnover (turnover efficiency).

Physical properties of alternatives to the fully halogenated chlorofluorocarbons

NASA Technical Reports Server (NTRS)

Mclinden, Mark O.

1990-01-01

Presented here are recommended values and correlations of selected physical properties of several alternatives to the fully halogenated chlorocarbons. The quality of the data used in this compilation varies widely, ranging from well-documented, high accuracy measurements from published sources to completely undocumented values listed on anonymous data sheets. That some of the properties for some fluids are available only from the latter type of source is clearly not the desired state of affairs. While some would reject all such data, the compilation given here is presented in the spirit of laying out the present state of knowledge and making available a set of data in a timely manner, even though its quality is sometimes uncertain. The correlations presented here are certain to change quickly as additional information becomes available.

Reformulation of Stmerin(®) D CFC formulation using HFA propellants.

PubMed

Murata, Saburo; Izumi, Takashi; Ito, Hideki

2013-01-01

Stmerin(®) D was reformulated using hydrofluoroalkanes (HFA-134a and HFA-227) as alternative propellants instead of chlorofluorocarbons (CFCs), where the active ingredients were suspended in mixed CFCs (CFC-11/CFC-12/CFC-114). Here, we report the suspension stability and spray performance of the original CFC formulation and a reformulation using HFAs. We prepared metered dose inhalers (MDI) using HFAs with different surfactants and co-solvents, and investigated the effect on suspension stability by visual testing. We found that the drug suspension stability was poor in both HFAs, but was improved, particularly for HFA-227, by adding a middle chain fatty acid triglycerides (MCT) to the formulation. However, the vapor pressure of HFA-227 is higher than a CFC mixture and this increased the fine particle dose (FPD). Spray performance was adjusted by altering the actuator configuration, and the performance of different actuators was tested by cascade impaction. We found the spray performance could be controlled by the configuration of the actuator. A spray performance comparable to the original formulation was obtained with a 0.8 mm orifice diameter and a 90° cone angle. These results demonstrate that the reformulation of Stmerin(®) D using HFA-227 is feasible, by using MCT as a suspending agent and modifying the actuator configuration.

EXPERIMENTAL INVESTIGATION OF PIC FORMATION ...

EPA Pesticide Factsheets

The report gives results of experiments to assess: (1) the effect of residual copper retained in an incineration facility on polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) formation during incineration of non-copper-containing chlorofluorocarbons (CFCs); and (2) the formation of chlorinated and aromatic products of incomplete combustion (PICs), including PCDD/PCDFs, during incineration of CFC recycling residue and hydrochlorofluorocarbons (HCFCs). High concentrations of PCDD/PCDFs (23,800 ng/dscm at 7% O2) measured in FY91 during incineration of CFC-12 in a turbulent flame reactor (TFR) could not be repeated in the present study. Repetition tests conducted in the same facility under similar operating conditions resulted in PCDD/PCDF concentrations of 118ng/dscm at 7% O2. However, results of the present study suggest that residual copper retained in an incineration facility possibly promotes the formation of PCDD/PCDFs during incineration of CFC-12 which does not contain copper. Tests conducted in the TFR resulted in measured PCDD/PCDF concentrations of 386-454 ng/dscm at 7% O2 during incineration of CFC-12 which followed incineration of copper-containing compounds. These results suggest that CFCs may best be incinerated in incinerators which do not treat any copper-containing waste prior to CFC incineration. Report available at NTIS as PB96152186. To share information

The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer

USGS Publications Warehouse

Reilly, Thomas E.; Plummer, Niel; Phillips, Patrick J.; Busenberg, Eurybiades

1994-01-01

Measurements of the concentrations of chlorofluorocarbons (CFCs), tritium, and other environmental tracers can be used to calculate recharge ages of shallow groundwater and estimate rates of groundwater movement. Numerical simulation also provides quantitative estimates of flow rates, flow paths, and mixing properties of the groundwater system. The environmental tracer techniques and the hydraulic analyses each contribute to the understanding and quantification of the flow of shallow groundwater. However, when combined, the two methods provide feedback that improves the quantification of the flow system and provides insight into the processes that are the most uncertain. A case study near Locust Grove, Maryland, is used to investigate the utility of combining groundwater age dating, based on CFCs and tritium, and hydraulic analyses using numerical simulation techniques. The results of the feedback between an advective transport model and the estimates of groundwater ages determined by the CFCs improve a quantitative description of the system by refining the system conceptualization and estimating system parameters. The plausible system developed with this feedback between the advective flow model and the CFC ages is further tested using a solute transport simulation to reproduce the observed tritium distribution in the groundwater. The solute transport simulation corroborates the plausible system developed and also indicates that, for the system under investigation with the data obtained from 0.9-m-long (3-foot-long) well screens, the hydrodynamic dispersion is negligible. Together the two methods enable a coherent explanation of the flow paths and rates of movement while indicating weaknesses in the understanding of the system that will require future data collection and conceptual refinement of the groundwater system.

New High-Resolution Absorption Cross-Section Measurements of HCFC-142B in the Mid-Ir

NASA Astrophysics Data System (ADS)

Le Bris, Karine; Strong, Kimberly; Melo, Stella

2009-06-01

HCFC-142b (1-chloro-1,1-difluoroethane) is a temporary substitute for ozone-depleting chlorofluorocarbons (CFCs). However, due to its high absorption cross-sections in the mid-IR, HCFC-142b is also a highly potent greenhouse gas, now detectable from space by satellite missions. So far, the accuracy of the retrieval has been limited by the lack of reference data in a range of temperatures compatible with atmospheric observations. We present new absorption cross section measurements of HCFC-142b at high-resolution (0.02 cm^{-1}) from 223 K to 283 K in the 600 cm^{-1}- 4000 cm^{-1} spectral window. The composite spectra are calculated for each temperature from a set of acquisitions at different pressures by Fourier transform spectroscopy.

Ion and Electron Interactions at Thermal and Suprathermal Energies

DTIC Science & Technology

1989-09-30

example, upper limits to the heats of formation of HPO, H2 PO , PCH 2 + and HCP have been obtained. The details are given in the research paper... formation requires that electronegative gases (such as O , halogens, chlorofluorocarbonsI be present. A multitude of excited states of A, and B2 and...6lal. A ’, -- A + B, Mutual neutralization The ternary process 6(b) c:ould ’esilt in the 6ihl. A’ - B_ - M- Ternjrv ionic formation of AB A- B. , +M

Analysis of diurnal variability of atmospheric halocarbons and CFC replacements to imply emission strength and sources at an urban site of Lukang in central Taiwan

NASA Astrophysics Data System (ADS)

Lee, Bing-Sun; Chiou, Chung-Biau; Lin, Chung-Yi

2014-12-01

Hourly atmospheric measurements of halocarbons and chlorofluorocarbon (CFC) replacements were conducted at an urban site of Lukang, Changhua, in central Taiwan from May to August, 2013. The temporal distribution of different groups of halocarbons in the Lukang urban atmosphere, including chlorofluorocarbons (CFCs), Chlorodifluoromethane (HCFC-22), Bromochlorodifluoromethane (Halon-1211), and other chlorinated compounds, is presented and discussed. The concentrations (mixing ratios) of HCFC-22, Dichlorodifluoromethane (CFC-12), Halon-1211, Trichlorofluoromethane (CFC-11), Dichloromethane (CH2Cl2), and Trichloroethylene (TCE) were enhanced with respect to the local background levels; the atmospheric mixing ratio of carbon tetrachloride (CCl4) was slightly higher than its local background level; on the other hand, 1,1,2-Trichlorotrifluoroethane (CFC-113) was relatively uniform and not very different from background atmospheric level in non-urban areas. Among these compounds, HCFC-22, Halon-1211 and the halogenated compounds, CH2Cl2 and TCE, used as solvents were strongly enhanced. The average mixing ratio of Halon-1211 was higher than the local background of ∼4.5 ppt by ∼60% although Halon-1211 production had been phased out by 1996. Hourly average mixing ratios of halocarbons (HCFC-22, CFC-12, Halon-1211, CFC-11, CH2Cl2, and TCE) illustrated a distinct diurnal cycle characterized with a pattern of elevated mixing ratio and large mixing ratio variability amplitude at night relative to that in daytime. Although emission sources of these halocarbons were complex, hourly average mixing ratios for most of these high variability halocarbons peaked at ∼5:00 AM when the hourly average wind speed reached the minimum value of the day; by contrast, the hourly average mixing ratio of CO peaked at ∼8:30 AM when the ambient atmospheric wind condition was strongly influenced by sea breezes during the traffic rush hours. This phenomenon revealed that meteorological factors predominated the distribution of halocarbon mixing ratio in the urban atmosphere and the traffic emission of CFC-12 derived from old vehicles manufactured before 1994 was insignificant to the CFC-12 mixing ratio in the urban atmosphere. The meteorological condition of nighttime atmospheric temperature inversion and low wind speed facilitated the accumulation of terrestrial airborne pollutants near the ground; consequently the hourly average mixing ratios at night were higher than those in daytime by up to ∼2% (CFC-11), ∼7% (CFC-12), ∼75% (HCFC-22), ∼72% (Halon-1211), ∼280% (CH2Cl2), and ∼155% (TCE).

Detecting Industrial Pollution in the Atmospheres of Earth-like Exoplanets

NASA Astrophysics Data System (ADS)

Lin, Henry W.; Gonzalez Abad, Gonzalo; Loeb, Abraham

2014-09-01

Detecting biosignatures, such as molecular oxygen in combination with a reducing gas, in the atmospheres of transiting exoplanets has been a major focus in the search for alien life. We point out that in addition to these generic indicators, anthropogenic pollution could be used as a novel biosignature for intelligent life. To this end, we identify pollutants in the Earth's atmosphere that have significant absorption features in the spectral range covered by the James Webb Space Telescope. We focus on tetrafluoromethane (CF4) and trichlorofluoromethane (CCl3F), which are the easiest to detect chlorofluorocarbons (CFCs) produced by anthropogenic activity. We estimate that ~1.2 days (~1.7 days) of total integration time will be sufficient to detect or constrain the concentration of CCl3F (CF4) to ~10 times the current terrestrial level.

Metabolism and toxicity of hydrochlorofluorocarbons: current knowledge and needs for the future.

PubMed Central

Anders, M W

1991-01-01

Hydrochlorofluorocarbons (HCFCs) are being developed as replacements for chlorofluorocarbons (CFCs) that deplete stratospheric ozone. The depletion of stratospheric ozone may increase the intensity of ultraviolet radiation at the earth's surface, which may be associated with global, adverse human health effects. The greater tropospheric lability of HCFCs, which is due to the presence of C-H bonds, reduces HCFC migration to the stratosphere; HCFCs should, therefore, cause less depletion of stratospheric ozone than CFCs. HCFCs under development include HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-132b (1,2-dichloro-1,1-difluoroethane), HCFC-134a (1,1,1,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane, and HCFC-142b (1-chloro-1,1-difluoroethane). With the exception of HCFC-22, which is already in use, the metabolism and toxicity of HCFCs have not been studied in detail. By analogy to chlorinated ethanes, predictions can be made about the possible metabolism of HCFCs, but there are insufficient data available to predict rates of metabolism. Although most HCFCs appear to show low acute toxicity, some HCFCs are mutagenic in the Ames test. Hence, future research on HCFCs should include studies on the in vivo and in vitro metabolism of HCFCs as well as on their toxicity in in vivo and in vitro systems. PMID:1820265

Metabolism and toxicity of hydrochlorofluorocarbons: current knowledge and needs for the future.

PubMed

Anders, M W

1991-12-01

Hydrochlorofluorocarbons (HCFCs) are being developed as replacements for chlorofluorocarbons (CFCs) that deplete stratospheric ozone. The depletion of stratospheric ozone may increase the intensity of ultraviolet radiation at the earth's surface, which may be associated with global, adverse human health effects. The greater tropospheric lability of HCFCs, which is due to the presence of C-H bonds, reduces HCFC migration to the stratosphere; HCFCs should, therefore, cause less depletion of stratospheric ozone than CFCs. HCFCs under development include HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-132b (1,2-dichloro-1,1-difluoroethane), HCFC-134a (1,1,1,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane, and HCFC-142b (1-chloro-1,1-difluoroethane). With the exception of HCFC-22, which is already in use, the metabolism and toxicity of HCFCs have not been studied in detail. By analogy to chlorinated ethanes, predictions can be made about the possible metabolism of HCFCs, but there are insufficient data available to predict rates of metabolism. Although most HCFCs appear to show low acute toxicity, some HCFCs are mutagenic in the Ames test. Hence, future research on HCFCs should include studies on the in vivo and in vitro metabolism of HCFCs as well as on their toxicity in in vivo and in vitro systems.

Metabolism and toxicity of hydrochlorofluorocarbons: Current knowledge and needs for the future

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

Anders, M.W.

1991-12-01

Hydrochlorofluorocarbons (HCFCs) are being developed as replacements for chlorofluorocarbons (CFCs) that deplete stratospheric ozone. The depletion of stratospheric ozone may increase in intensity of ultraviolet radiation at the earth's surface, which may be associated with global, adverse human health effects. The greater tropospheric lability of HCFCs, which is due to the presence of C-H bonds, reduces HCFC migration to the stratosphere; HCFCs should, therefore, cause less depletion of stratospheric ozone than CFCs. HCFCs under development include HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-132b (1,2-dichloro-1,1-difluoroethane), HCFC-134a (1,1,1,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), and HCFC-142b (1-chloro-1,1-difluoroethane). With the exception of HCFC-22, which is already in use, themore » metabolism and toxicity of HCFCs have not been studied in detail. By analogy to chlorinated ethanes, predictions can be made about the possible metabolism of HCFCs, but there are insufficient data available to predict rates of metabolism. Although most HCFCs appear to show low acute toxicity, some HCFCs are mutagenic in the Ames test. Hence, future research on HCFCs should include studies on the in vivo and in vitro metabolism of HCFCs as well as on their toxicity in in vivo and in vitro systems. 63 refs., 4 figs., 1 tab.« less

Satellite observations of stratospheric hydrogen fluoride and comparisons with SLIMCAT calculations

NASA Astrophysics Data System (ADS)

Harrison, J. J.; Chipperfield, M. P.; Boone, C. D.; Dhomse, S. S.; Bernath, P. F.; Froidevaux, L.; Anderson, J.; Russell, J., III

2015-12-01

The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone, and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of HF, the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing instruments ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer), which has been recording atmospheric spectra since 2004, and HALOE (HALogen Occultation Experiment), which recorded atmospheric spectra between 1991 and 2005, with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the agreement between observation and model is good, although the ACE-FTS measurements are biased high by ∼ 10 % relative to HALOE. The observed global HF trends reveal a substantial slowing down in the rate of increase of HF since the 1990s: 4.97 ± 0.12 % year-1 (1991-1997; HALOE), 1.12 ± 0.08 % year-1 (1998-2005; HALOE), and 0.52 ± 0.03 % year-1 (2004-2012; ACE-FTS). In comparison, SLIMCAT calculates trends of 4.01, 1.10, and 0.48 % year-1, respectively, for the same periods; the agreement is very good for all but the earlier of the two HALOE periods. Furthermore, the observations reveal variations in the HF trends with latitude and altitude, for example between 2004 and 2012 HF actually decreased in the Southern Hemisphere below ∼ 35 km. SLIMCAT calculations broadly agree with these observations, most notably between 2004 and 2012. Such variations are attributed to variability in stratospheric dynamics over the observation period.

Dating groundwater with dissolved silica and CFC concentrations in crystalline aquifers.

PubMed

Marçais, Jean; Gauvain, Alexandre; Labasque, Thierry; Abbott, Benjamin W; Pinay, Gilles; Aquilina, Luc; Chabaux, François; Viville, Daniel; de Dreuzy, Jean-Raynald

2018-09-15

Estimating intermediate water residence times (a few years to a century) in shallow aquifers is critical to quantifying groundwater vulnerability to nutrient loading and estimating realistic recovery timelines. While intermediate groundwater residence times are currently determined with atmospheric tracers such as chlorofluorocarbons (CFCs), these analyses are costly and would benefit from other tracer approaches to compensate for the decreasing resolution of CFC methods in the 5-20 years range. In this context, we developed a framework to assess the capacity of dissolved silica (DSi) to inform residence times in shallow aquifers. We calibrated silicate weathering rates with CFCs from multiple wells in five crystalline aquifers in Brittany and in the Vosges Mountains (France). DSi and CFCs were complementary in determining apparent weathering reactions and residence time distributions (RTDs) in shallow aquifers. Silicate weathering rates were surprisingly similar among Brittany aquifers, varying from 0.20 to 0.23 mg L -1  yr -1 with a coefficient of variation of 7%, except for the aquifer where significant groundwater abstraction occurred, where we observed a weathering rate of 0.31 mg L -1  yr -1 . The silicate weathering rate was lower for the aquifer in the Vosges Mountains (0.12 mg L -1  yr -1 ), potentially due to differences in climate and anthropogenic solute loading. Overall, these optimized silicate weathering rates are consistent with previously published studies with similar apparent ages range. The consistency in silicate weathering rates suggests that DSi could be a robust and cheap proxy of mean residence times for recent groundwater (5-100 years) at the regional scale. This methodology could allow quantification of seasonal groundwater contributions to streams, estimation of residence times in the unsaturated zone and improve assessment of aquifer vulnerability to anthropogenic pollution. Copyright © 2018 Elsevier B.V. All rights reserved.

Application of environmental tracers to delineate recharge patterns and nitrate contamination in shallow groundwater around a river

NASA Astrophysics Data System (ADS)

Kaown, Dugin; Koh, Eunhee; Park, Byeong-Hak; Lee, Kang-Kun

2016-04-01

Hydrogeochemical data, stable isotopes, chlorofluorocarbon (CFCs) and 3H-3He in groundwater were applied to characterize residence time, recharge patterns and nitrate contamination of groundwater in a small agricultural area, Yangpyung, Korea. The study area is located around a river and the measured groundwater table ranges from 1.5 to 2.65 m during the year. Most residents in the study area practice agriculture and potato, strawberry, and cabbage are the typical vegetables grown. Vegetable fields are mostly located in the upgradient area of the study area while forest and residence areas are located in the downgradient area. A lot of chemical and organic fertilizers are applied in the upgradient area. The concentration of NO3-N in groundwater showed 9.8-83.7 mg/L in the upgradient area and 0.1-22.6 mg/L in the downgradient area in 2014. It is necessary to monitor groundwater recharge patterns and transport processes of nitrate to protect surface water around the study area. The values of δ18O and δD showed that groundwater is recharged mainly from summer precipitation. The apparent groundwater ages using 3H-3He and CFCs ranged from 13 to 27 years in the upgradient area and from 25 to 35 years in the downgradient area. The NO3-N in more recently recharged groundwater showed higher concentrations while the NO3-N in older groundwater showed low concentrations. Some shallow wells in the downgradient area showed similar apparent groundwater age with that of the river water indicating groundwater-surface water interactions. A conceptual model of groundwater-surface water interactions using stable isotopes, apparent 3H-3He and CFCs age in groundwater will be useful to understand the hydrological processes and nitrate contamination of the study area.

A two-dimensional model with coupled dynamics, radiative transfer, and photochemistry. 2: Assessment of the response of stratospheric ozone to increased levels of CO2, N2O, CH4, and CFC

NASA Technical Reports Server (NTRS)

Schneider, Hans R.; Ko, Malcolm K. W.; Shia, Run-Lie; Sze, Nien-Dak

1993-01-01

The impact of increased levels of carbon dioxide (CO2), chlorofluorocarbons (CFCs), and other trace gases on stratospheric ozone is investigated with an interactive, two-dimensional model of gas phase chemistry, dynamics, and radiation. The scenarios considered are (1) a doubling of the CO2 concentration, (2) increases of CFCs, (3) CFC increases combined with increases of nitrous oxide (N2O) and methane CH4, and (4) the simultaneous increase of CO2, CFCs, N2O, and CH4. The radiative feedback and the effect of temperature and circulation changes are studied for each scenario. For the double CO2 calculations the tropospheric warming was specified. The CO2 doubling leads to a 3.1% increase in the global ozone content. Doubling of the CO2 concentrations would lead to a maximum cooling of about 12 C at 45 km if the ozone concentration were held fixed. The cooling of the stratosphere leads to an ozone increase with an associated increase in solar heating, reducing the maximum temperature drop by about 3 C. The CFC increase from continuous emissions at 1985 rate causes a 4.5% loss of ozone. For the combined perturbations a net loss of 1.3% is calculated. The structure of the perturbations shows a north-south asymmetry. Ozone losses (when expressed in terms of percent changes) are generally larger in the high latitudes of the southern hemisphere as a result of the eddy mixing being smaller than in the northern hemisphere. Increase of chlorine leads to ozone losses above 30 km altitude where the radiative feedback results in a cooler temperature and an ozone recovery of about one quarter of the losses predicted with a noninteractive model. In all the cases, changes in circulation are small. In the chlorine case, circulation changes reduce the calculated column depletion by about one tenth compared to offline calculations.

Aquifer susceptibility in Virginia, 1998-2000

USGS Publications Warehouse

Nelms, David L.; Harlow, George E.; Plummer, Niel; Busenberg, Eurybiades

2003-01-01

The U.S. Geological Survey (USGS), in cooperation with the Virginia Department of Health, sampled water from 171 wells and springs across the Commonwealth of Virginia between 1998 and 2000 as part of the Virginia Aquifer Susceptibility study. Most of the sites sampled are public water supplies that are part of the comprehensive Source Water Assessment Program for the Commonwealth. The fundamental premise of the study was that the identification of young waters (less than 50 years) by multiple environmental tracers could be used as a guide for classifying aquifers in terms of susceptibility to contamination from near-surface sources. Environmental tracers, including chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and tritium/helium-3 (3H/3He), and carbon isotopes (14C and d13C) were used to determine the age of water discharging from wells and springs. Concentrations of CFCs greater than 5 picograms per kilogram and 3H concentrations greater than 0.6 tritium unit were used as thresholds to indicate that parts of the aquifer sampled have a component of young water and are, therefore, susceptible to near-surface contamination. Concentrations of CFCs exceeded the susceptibility threshold in 22 percent of the wells and in one spring sampled in the Coastal Plain regional aquifer systems. About 74 percent of the samples from wells with the top of the first water zone less than 100 feet below land surface exceeded the threshold values, and water supplies developed in the upper 100 feet of the Coastal Plain are considered to be susceptible to contamination from near-surface sources. The maximum depth to the top of the screened interval for wells that contained CFCs was less than 150 feet. Wells completed in the deep confined aquifers in the Coastal Plain generally contain water older than 1,000 years, as indicated by carbon-14 dating, and are not considered to be susceptible to contamination under natural conditions. All of the water samples from wells and springs in the fractured-rock terrains (the Appalachian Plateaus, Valley and Ridge, Blue Ridge, and Piedmont regional aquifer systems) contained concentrations of CFCs and 3H greater than one or both of the thresholds. Because all of the water samples exceeded at least one of the threshold values, young water is present throughout most of these regional aquifer systems; therefore, water supplies developed in these systems are susceptible to contamination from near-surface sources. No relation between well depth and presence of CFCs is evident from samples in the fractured-rock terrains. More than 95 percent of the samples for which the dating methods were applicable contained waters with apparent ages less than 35 years. About 5 percent of these samples, most of which were from the Blue Ridge and Piedmont regional aquifer systems, contained young waters with apparent ages of less than 5 years. Most of the samples from the Valley and Ridge Carbonate, Blue Ridge, and Piedmont regional aquifer systems had young water fractions of more than 50 percent, whereas samples from the Coastal Plain Shallow and Appalachian Plateaus regional aquifer systems contained less than 40 percent young waters. Concentrations of CFCs in excess of air-water equilibrium, which can indicate that nonatmospheric sources (such as sewage effluent) have introduced CFCs into the ground-water system, were measured in 6 and 48 percent of the water samples from the Coastal Plain and fractured-rock regional aquifer systems, respectively. The nitrate (NO3) concentrations greater than the USGS detection level of 0.05 milligrams per liter generally increase as the apparent age of the young water fraction decreases, with the highest NO3 concentrations for samples in which one or more of the CFCs are above modern atmospheric mixing ratios (commonly referred to as 'contaminated' for ground-water dating purposes). Most of the samples in which NO3 was detected w

DETECTING INDUSTRIAL POLLUTION IN THE ATMOSPHERES OF EARTH-LIKE EXOPLANETS

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

Lin, Henry W.; Abad, Gonzalo Gonzalez; Loeb, Abraham, E-mail: henrylin@college.harvard.edu, E-mail: ggonzalezabad@cfa.harvard.edu, E-mail: aloeb@cfa.harvard.edu

Detecting biosignatures, such as molecular oxygen in combination with a reducing gas, in the atmospheres of transiting exoplanets has been a major focus in the search for alien life. We point out that in addition to these generic indicators, anthropogenic pollution could be used as a novel biosignature for intelligent life. To this end, we identify pollutants in the Earth's atmosphere that have significant absorption features in the spectral range covered by the James Webb Space Telescope. We focus on tetrafluoromethane (CF{sub 4}) and trichlorofluoromethane (CCl{sub 3}F), which are the easiest to detect chlorofluorocarbons (CFCs) produced by anthropogenic activity. Wemore » estimate that ∼1.2 days (∼1.7 days) of total integration time will be sufficient to detect or constrain the concentration of CCl{sub 3}F (CF{sub 4}) to ∼10 times the current terrestrial level.« less

Tracer signals of the intermediate layer of the Arabian Sea

NASA Astrophysics Data System (ADS)

Rhein, Monika; Stramma, Lothar; Plähn, Olaf

In 1995, hydrographic and chlorofluorocarbon (CFCs, components F11, F12) measurements were carried out in the Gulf of Aden, in the Gulf of Oman, and in the Arabian Sea. In the Gulf of Oman, the F12 concentrations in the Persian Gulf outflow (PGW) at about 300m depth were significantly higher than in ambient surface water with saturations reaching 270%. These high values could not be caused by air-sea gas exchange. The outflow was probably contaminated with oil, and the lipophilic character of the CFCs could then lead to the observed supersaturations. The intermediate F12 maximum decreased rapidly further east and south. At the Strait of Bab el Mandeb in the Gulf of Aden, the Red Sea outflow (RSW) was saturated with F12 to about 65% at 400m depth, and decreased to 50% while descending to 800m depth. The low saturation is not surprising, because the outflow contains deep and intermediate water masses from the Red Sea which were isolated from the surface for some time. The tracer contributions to the Arabian Sea for Indian Central Water (ICW) and PGW are about equal, while below 500m depth the RSW contribution greatly exceeds ICW. Modeling the CFC budget of the Arabian Sea, the inflow of ICW north of 12°N is estimated to be 1-6 Sv, depending mainly on the strength of the flow of Red Sea Water into the Arabian Sea.

Effect of Dynamic Pressure on the Performance of Thermoacoustic Refrigerator with Aluminium (Al) Resonator

NASA Astrophysics Data System (ADS)

Arya, Bheemsha; Nayak, B. Ramesh; Shivakumara, N. V.

2018-04-01

In practice the refrigerants are being used in the conventional refrigeration system to get the required cooling effect. These refrigerants produce Chlorofluorocarbons (CFCs) and Hydro chlorofluorocarbons (HCFCs) which are highly harmful to the environment, particularly depleting of ozone layers resulting in green house emissions. In order to overcome these effects, the research needs to be focused on the development of an ecofriendly refrigeration system. The thermoacoustic refrigeration system is one among such system where the sound waves are used to compress and expand the gas particles. This study focuses on the effect of dynamic pressure on the thermoacoustic refrigerator made of aluminium with overall length of 748.82 mm, and the entire inner surface of the resonator tube was coated with 2mm thickness of polyurethane to minimize the heat losses to the atmosphere. Experiments were conducted with different stack geometries i.e. parallel plates having 0.119 mm thick with spacing between the plates maintained at 0.358 mm, 1mm diameter pipes, 2mm diameter pipes and 4 mm diameter pipes. Experiments were also conducted with different drive ratios of 0.6%, 1% and 1.6% for a constant dynamic pressure of 2 bar and 10 bar for helium and air as working medium. The results were plotted with the help of graphs, the variation of coefficient of performance (COP) and the relative coefficient of performance (COPR) for the above said conditions were calculated.

Multimodel Estimates of Atmospheric Lifetimes of Long-lived Ozone-Depleting Substances: Present and Future

NASA Technical Reports Server (NTRS)

Chipperfield, M. P.; Liang, Q.; Strahan, S. E.; Morgenstern, O.; Dhomse, S. S.; Abraham, N. L.; Archibald, A. T.; Bekki, S.; Braesicke, P.; Di Genova, G.;

Multimodel Estimates of Atmospheric Lifetimes of Long-Lived Ozone-Depleting Substances: Present and Future

NASA Technical Reports Server (NTRS)

Chipperfield, M. P.; Liang, Q.; Strahan, S. E.; Morgenstern, O.; Dhomse, S. S.; Abraham, N. L.; Archibald, A. T.; Bekki, S.; Braesicke, P.; Di Genova, G.;

Ethylene oxide sterilization: how hospitals can adapt to the changes.

PubMed

1994-12-01

Ethylene oxide (EtO) gas sterilizers have been used by hospitals for over 40 years to sterilize surgical equipment and supplies that are heat sensitive or that cannot tolerate excessive moisture. However, in recent decades, EtO has been recognized as a potential mutagenic, reproductive, neurologic, and fire and explosion hazard to workers, and one agency has reportedly voted to classify EtO as carcinogenic to humans. Strict regulations concerning EtO exposure have been imposed by the Occupational Safety and Health Administration (OSHA), and the use of EtO, along with other toxic pollutants, is also being monitored by the Environmental Protection Agency (EPA) under the Clean Air Act. In addition, the use of chlorofluorocarbons (CFCs) as EtO diluents has focused attention on the EtO-CFC mixtures used in many sterilizers because CFCs have been linked to destruction of the ozone layer. Concerns about restrictive regulations related to these issues have prompted many hospitals to examine their use of EtO sterilization and propagated the misinformation that EtO sterilization is being phased out. In this article, we address some commonly asked questions regarding the use and regulation of EtO mixtures, as well as alternative sterilization agents and methods; provide two case studies illustrating how hospitals can evaluate various sterilization options; and summarize our conclusions and recommendations for hospitals facing decisions about sterilization techniques. For related topics, also see our Evaluation Update on endoscope reprocessors and our Hazard Report on improperly connected EtO-CFC cylinders to EtO sterilizers in this issue.

Volatile Release from the Siberian Traps Inferred from Melt Inclusions

NASA Astrophysics Data System (ADS)

Black, B. A.; Elkins-Tanton, L. T.; Rowe, M. C.; Ukstins Peate, I.

2009-12-01

The Siberian Traps Large Igneous Province is one of the largest known continental flood volcanic provinces in the Phanerozoic. The quantification of volatile degassing is particularly important because the Siberian Traps have often been invoked as a possible trigger for the end-Permian mass extinction (e.g. Campbell et al., 1992; Wignall, 2001). Volatile degassing provides a crucial mechanism to link mafic volcanic eruption to global environmental change. Mafic flood basalt magmas are expected to have low volatile contents (similar to mid-ocean ridge basalts). However, Siberian Traps magmas were chambered in and erupted through a thick sedimentary basin and may have interacted with, and obtained volatiles from, sedimentary lithologies such as limestone, coal, and evaporite. Melt inclusions from the Siberian Traps provide insight into the potential total volatile budget throughout the evolution of the large igneous province. These droplets of trapped melt may preserve volatile species that would otherwise have degassed at the time of eruption (Thordarson et al., 1996). Mafic pyroclastic deposits from the lowermost Arydzhangsky suite (basal Siberian Traps) contain clinopyroxene phenocrysts hosting melt inclusions. Electron microprobe analysis of clinopyroxene-hosted re-homogenized melt inclusions indicates maximum measured concentrations of up to 1500 - 2000 ppm sulfur, 500 - 760 ppm chlorine, and 1900 - 2400 ppm fluorine. Olivines from the Maymechinsky suite, recognized as the last extrusive products of Siberian Traps volcanism, contain melt inclusions with maximum sulfur concentrations in the range of 5000 ppm, and less substantial concentrations of chlorine and fluorine. Intrusive igneous rocks from the province also display significant volatile contents. A sill from the Ust-Ilimsk region yielded plagioclase-hosted melt inclusions which contain chlorine and fluorine concentrations nearing one weight percent. Visscher et al. (2004) proposed that chlorofluorocarbon compounds (CFCs) may have played a major role in the terrestrial end-Permian extinction. These CFCs are powerful catalysts for the breakdown of ozone, a process which can expose the biosphere to increased ultraviolet radiation. Measurements of elevated chlorine and fluorine from the Siberian Traps may thus provide a concrete source for CFCs that could have triggered this kill mechanism.

Economics of "essential use exemptions" for metered-dose inhalers under the Montreal Protocol.

PubMed

DeCanio, Stephen J; Norman, Catherine S

2007-10-01

The Montreal Protocol on Substances that Deplete the Ozone Layer has led to rapid reductions in the use of ozone-depleting substances worldwide. However, the Protocol provides for "essential use exemptions" (EUEs) if there are no "technically and economically feasible" alternatives. An application that might qualify as an "essential use" is CFC-powered medical metered-dose inhalers (MDIs) for the treatment of asthma and chronic obstructive pulmonary disease (COPD), and the US and other nations have applied for exemptions in this case. One concern is that exemptions are necessary to ensure access to medications for low-income uninsureds. We examine the consequences of granting or withholding such exemptions, and conclude that government policies and private-sector programs are available that make it economically feasible to phase out chlorofluorocarbons (CFCs) in this application, thereby furthering the global public health objectives of the Montreal Protocol without compromising the treatment of patients who currently receive medication by means of MDIs.

Tropospheric Halogen Chemistry

NASA Astrophysics Data System (ADS)

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

2003-12-01

Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other 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 hydrocarbons. Loss of ozone by catalytic reactions involving halogen radicals lowers the concentrations of the hydroxyl radical OH and thus the oxidation power of the atmosphere. Figure 1 shows these and other relevant halogen-related processes schematically. The sum of particulate and gaseous halogen concentrations maximize in the marine troposphere. Important for our climate - via feedback with cloud microphysics mainly in the large regions of marine stratocumulus - are links between halogen chemistry and the sulfur cycle. HOBraq and HOClaq can increase the liquid phase oxidation of S(IV) to S(VI), while BrO can decrease the most important in situ source for SO2 in the marine troposphere, namely, the oxidation of DMS to SO2 by reaction with OH by providing an alternate pathway (BrO+DMS) that reduces the yield of SO2 from DMS oxidation. Thus, the presence of bromine and chlorine in the troposphere lowers gas phase SO2 concentrations and thus the formation of new sulfate particles via the reaction sequence SO2+OH→H2SO4. (17K)Figure 1. Schematic depiction of the most important halogen-related processes in the troposphere. High mixing ratios of iodine oxide at a coastal site indicate a potentially significant role of iodine for the destruction of O3 and new particle embryo formation (Alicke et al., 1999; O'Dowd et al., 1998). Almost 20 years earlier, Chameides and Davis (1980) suggested that open ocean iodine chemistry would be initiated by the photolysis of CH3I. This was based on the measurements of Lovelock et al. (1973) and Singh et al. (1979), who found volume mixing ratios of CH3I of 1-5 pmol mol-1 over the ocean.The potentially strong involvement of halogens in tropospheric chemistry was first observed in the Arctic, where strong ozone depletion events were found to coincide with high levels of bromine (Barrie et al., 1988).The first mid-latitude demonstration of reactive halogen chemistry in the troposphere was made downwind of salt pans in the Dead Sea area, where the so far highest atmospheric mixing ratios of BrO were measured (Hebestreit et al., 1999). Volcanoes are sources of halogens as well, mainly in the form of HCl. Biomass burning releases halogens as do industrial processes.So far we have only mentioned chlorine, bromine, and iodine. This is justified because chemistry of fluorine is of no consequence, as very unreactive HF is efficiently formed in the atmosphere, e.g., via the reaction F+H2O→HF+OH. However, several fluorine-containing gases of anthropogenic origin are potentially powerful greenhouse gases, because they absorb strongly in the infrared atmospheric window region near 10 μm. Fully fluorinated gases - such as SF6, CF4, and C2F6 - have atmospheric lifetimes of the order of thousands of years and thus possess very high global warming potential (GWP). Although their abundance in the atmosphere has not yet grown large enough to be of concern for Earth's climate, their production must ultimately be curtailed in the future. The most abundant fully fluorinated gas, CF4, had an atmospheric volume mixing ratio of ˜75 pmol mol-1 in 1995 (Warneck, 1999). Because of their higher concentrations in the atmosphere, about 270 pmol mol-1 and 530 pmol mol-1, respectively, the CFC gases, CFCl3 and CF2Cl2, already exert a significant radiative greenhouse forcing (Ramanathan, 1975) on Earth's climate. For further discussion about atmospheric fluorine, the reader is referred to a thorough review article by Harnisch (1999).Several overview articles have been published on tropospheric halogen chemistry since the early 1980s, starting with Cicerone (1981). Wayne et al. (1995) list in great detail reaction paths, laboratory data, and atmospheric implications of halogen oxides. A good overview on laboratory measurements was also given by de Haan et al. (1999). Reaction cycles involved in tropospheric halogen chemistry and measurements are also thoroughly discussed by Platt (2000) and Platt and Hönninger (2003). Important compilations of laboratory studies that were made to elucidate chemical reaction paths are given by, e.g., DeMore et al. (1997), Sander et al. (2000), and Atkinson et al. (1999, 2000). Emission inventories for chlorine were compiled by Graedel and Keene (1995) and Keene et al. (1999).In Section 4.02.2 of this overview we will first describe the main halogen reaction mechanisms and then discuss, in Section 4.02.3, the springtime surface ozone depletion events in high latitudes that were first observed in the Arctic. Another main part of this chapter is concerned with halogens in the marine boundary layer ( Section 4.02.4). In Section 4.02.5 we describe interactions of halogens with some other elements of atmospheric importance. A very recently discovered environment where halogen chemistry plays a large role are salt lakes ( Section 4.02.6). There the chemistry bears similarity to that of the high-latitude ozone depletion events. This is followed in Section 4.02.7 by a discussion of halogen chemistry in the free troposphere and in Section 4.02.8 by other sources of halogens such as industry and biomass burning.

Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

USGS Publications Warehouse

Shapiro, S.D.; Busenberg, E.; Focazio, M.J.; Plummer, Niel

2004-01-01

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl4), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl4, chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl4 and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl4 and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources. ?? 2003 Elsevier B.V. All rights reserved.

Transport and degradation of chlorofluorocarbons (CFCs) in the pyritic Rabis Creek aquifer, Denmark

NASA Astrophysics Data System (ADS)

Hinsby, K.; HøJberg, Anker L.; Engesgaard, P.; Jensen, K. H.; Larsen, F.; Plummer, L. N.; Busenberg, E.

2007-10-01

Vertical profiles of the chlorofluorocarbons CFC-11, CFC-12, and CFC-113 penetrating aerobic and anaerobic parts of a shallow sandy aquifer show that the CFC gases are degraded in the <1 m thick transition zone from aerobic to anaerobic groundwater in a pyritic sand aquifer at Rabis Creek, Denmark. Two-dimensional solute transport simulations with either zero-order or first-order degradation in the anaerobic zone corroborate this interpretation. The transport model was previously calibrated against detailed tritium profiles in the same wells. First-order degradation is found to best match the observed CFC profiles yielding an approximate half-life of a few months for CFC-11. Degradation is not as clearly recognized for CFC-12 and CFC-113, but it may occur with rates corresponding to a half-life of a few years or more. Data indicate a geochemical control of the CFC concentration gradient at the redox front and that denitrification and denitrifiers are not of major importance for the observed CFC degradation. The responsible mechanism behind the observed degradation is not known but we suggest that reductive dehalogenation by surface-bound Fe(II) on pyrite possibly enhanced by the presence of Fe(III)-bearing weathering products (green rust) may be a plausible mechanism. The observed data and the performed simulations confirm the potential application of the CFC gases as age-dating tools in the aerobic part of the investigated aquifer, but also that CFC data must be analyzed carefully before it is used as a dating tool in reducing aquifers because degradation may have occurred. The use of multiple or alternative tracers should be considered in anaerobic environments.

Linking chloride mass balance infiltration rates with chlorofluorocarbon and SF6 groundwater dating in semi-arid settings: potential and limitations.

PubMed

Stadler, Susanne; Osenbruck, Karsten; Duijnisveld, Wilhelmus H M; Schwiede, Martin; Bottcher, Jurgen

2010-09-01

In the framework of the investigation of enrichment processes of nitrate in groundwater of the Kalahari of Botswana near Serowe, recharge processes were investigated. The thick unsaturated zone extending to up to 100 m of mostly unconsolidated sediments and very low recharge rates pose a serious challenge to study solute transport related to infiltration and recharge processes, as this extends past the conventional depths of soil scientific investigations and is difficult to describe using evidence from the groundwater due to the limitations imposed by available tracers. To determine the link between nitrate in the vadose zone and in the uppermost groundwater, sediment from the vadose zone was sampled up to a depth of 15-20 m (in one case also to 65 m) on several sites with natural vegetation in the research area. Among other parameters, sediment and water were analysed to determine chloride and nitrate concentration depth profiles. Using the chloride mass balance method, an estimation of groundwater infiltration rates produced values of 0.2-4 mm a(-1). The uncertainty of these values is, however, high. Because of the extreme thickness of the vadose zone, the travel time in the unsaturated zone might reach extreme values of up to 500 years and more. For investigations using groundwater, we applied the chlorofluorocarbons CFC-113, CFC-12, sulphur hexafluoride (SF(6)) and tritium to identify potential recharge, and found indications for some advective transport of the CFCs and SF(6), which we accounted for as constituting potential active localised recharge. In our contribution, we show the potential and limitations of the applied methods to determine groundwater recharge and coupled solute transport in semi-arid settings, and compare travel time ranges derived from soil science and groundwater investigations.

Transport and degradation of chlorofluorocarbons (CFCs) in the pyritic Rabis Creek aquifer, Denmark

USGS Publications Warehouse

Hinsby, K.; Højberg, Anker L.; Engesgaard, P.; Jensen, K.H.; Larsen, F.; Plummer, Niel; Busenberg, Eurybiades

2007-01-01

Vertical profiles of the chlorofluorocarbons CFC‐11, CFC‐12, and CFC‐113 penetrating aerobic and anaerobic parts of a shallow sandy aquifer show that the CFC gases are degraded in the <1 m thick transition zone from aerobic to anaerobic groundwater in a pyritic sand aquifer at Rabis Creek, Denmark. Two‐dimensional solute transport simulations with either zero‐order or first‐order degradation in the anaerobic zone corroborate this interpretation. The transport model was previously calibrated against detailed tritium profiles in the same wells. First‐order degradation is found to best match the observed CFC profiles yielding an approximate half‐life of a few months for CFC‐11. Degradation is not as clearly recognized for CFC‐12 and CFC‐113, but it may occur with rates corresponding to a half‐life of a few years or more. Data indicate a geochemical control of the CFC concentration gradient at the redox front and that denitrification and denitrifiers are not of major importance for the observed CFC degradation. The responsible mechanism behind the observed degradation is not known but we suggest that reductive dehalogenation by surface‐bound Fe(II) on pyrite possibly enhanced by the presence of Fe(III)‐bearing weathering products (green rust) may be a plausible mechanism. The observed data and the performed simulations confirm the potential application of the CFC gases as age‐dating tools in the aerobic part of the investigated aquifer, but also that CFC data must be analyzed carefully before it is used as a dating tool in reducing aquifers because degradation may have occurred. The use of multiple or alternative tracers should be considered in anaerobic environments.

Application of magnetic resonance imaging to the investigation of the diffusivity of 1,1,1,2-tetrafluorethane in two polymers.

PubMed

Mayele, M; Oellrich, L R

2004-03-01

In order to evaluate the suitability of a polymer as a sealing material for certain working fluids used in process plants, information about the fluid diffusivity into the polymer or the polymer permeability to the fluid is a prerequisite. The fluid of interest in the present work is 1,1,1,2-tetrafluorethane, CH(2)FCF(3), a partly fluorinated hydrocarbon (HFC) commonly known as refrigerant R134a. HFCs are increasingly used in refrigeration, air conditioning, and heat pump applications as substitutes for the chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs) that are believed to be responsible for ozone depletion in the stratosphere. The polymers studied were FPM, a perfluoroelastomer, and EPDM, an ethylene-propylene-diene rubber. The study was carried out using magnetic resonance imaging (MRI). The contact time dependence of diffusion of the fluid into the polymer, as well as the spatial distributions of spin-lattice, T(1), and spin-spin, T(2), relaxation times, were used as indicators of the influence of the EPDM matrix on the mobility of R134a molecules.

Preliminary study of a gas burner-driven and ground-coupled heat pump system

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

Hsu, P.F.

1995-12-31

To address the concerns for higher energy efficiency and the immediate phase out of the chlorofluorocarbons (CFCs), a new gas burner-driven, ground-coupled heat pump (GBGCHP) system is proposed for study. The new system is energy efficient and pose no environmental problem. There are three unique features in the proposed system: (1) a patented gas burner-driven compressor with a floating diaphragm piston-cylinder for energy efficiency and accommodating variable load, (2) the ground coupled water-to-air heat exchangers for high coefficient of performance (COPs), and (3) the new refrigerants based on fluoroiodocarbons (FICS) with very little ozone depletion and global warming potential. Amore » preliminary analysis of a prototype heat pump with 3 ton (10.55 kW) heating capacity is presented. The thermodynamics analysis of the system shows that the steady state COP rating higher than 7 is possible with the system operating in heating mode. Additional research work for the GBGCHP system, especially the FICs` thermodynamic properties in the superheated region, is also described.« less

UV-B Radiation Contributes to Amphibian Population Declines

NASA Astrophysics Data System (ADS)

Blaustein, Andrew

2007-05-01

UV-B (280-315 nm) radiation is the most significant biologically damaging radiation at the terrestrial surface. At the organismal level, UV-B radiation can slow growth rates, cause immune dysfunction and result in sublethal damage. UV-B radiation can lead to mutations and cell death. Over evolutionary time, UV radiation has been an important stressor on living organisms. Natural events, including impacts from comets and asteroids, volcanic activity, supernova explosions and solar flares, can cause large-scale ozone depletion with accompanying increases in UV radiation. However, these natural events are transient. Moreover, the amount of ozone damage due to natural events depends upon a number of variables, including the magnitude of the event. This is different from modern-day human-induced production of chlorofluorocarbons (CFCs) and other chemicals that deplete stratospheric ozone continuously, resulting in long-term increases in UV-B radiation at the surface of the earth. We will briefly review the effects of UV-B exposure in one group of aquatic organisms_amphibians. UV-B has been implicated as a possible factor contributing to global declines and range reductions in amphibian populations.

What would have happened to the ozone layer if chlorofluorocarbons (CFCs) had not been regulated?

NASA Astrophysics Data System (ADS)

Oman, L.; Newman, P. A.; Douglass, A. R.; Fleming, E. L.; Frith, S. M.; Hurwitz, M.; Kawa, S. R.; Jackman, C. H.; Krotkov, N. A.; Nash, E. R.; Nielsen, J. E.; Pawson, S.; Stolarski, R. S.; Velders, G. J.

2010-12-01

The Montreal Protocol on Substances that Deplete the Ozone Layer was negotiated in 1987 and by 2010 had been signed by all of the nations of the world. In this presentation we use a fully coupled radiation-chemical-dynamical model to simulate a future world where ozone depletion substances (ODSs) were never regulated. In this “world avoided” simulation, ODS levels increase by 3% per year. From 1980 to 2020 we find that 17% of the globally average column ozone is destroyed, and from 1980 to 2065 67% is destroyed. Severe polar depletions (e.g., the Antarctic ozone hole) become year-round rather than just seasonal. Ozone levels in the tropical lower stratosphere remain constant until about 2053 and then collapse to near zero by 2058 as a result of heterogeneous chemical processes (as currently observed in the Antarctic ozone hole). The tropical cooling that triggers the ozone collapse is caused by an increase of the tropical lower stratospheric upwelling. In response to ozone changes, ultraviolet (UV) radiation increases, tripling the erythemal (sunburn) radiation in the northern summer mid-latitudes by 2065.

Volatile Release From The Siberian Traps Inferred From Melt Inclusions

NASA Astrophysics Data System (ADS)

Black, Benjamin A.; Elkins-Tanton, Linda T.; Rowe, Michael C.; Ukstins Peate, Ingrid

2010-05-01

The Siberian Traps Large Igneous Province is one of the largest known continental flood volcanic provinces in the Phanerozoic. The quantification of volatile degassing is particularly important because the Siberian Traps have often been invoked as a possible trigger for the end-Permian mass extinction (e.g. Campbell et al., 1992; Wignall, 2001). Volatile degassing provides a crucial mechanism to link mafic volcanic eruption with global environmental change. Mafic flood basalt magmas are expected to have low volatile contents (similar to mid-ocean ridge basalts). However, Siberian Traps magmas were chambered in and erupted through a thick sedimentary basin and may have interacted with, and obtained volatiles from, sedimentary lithologies such as limestone, coal, and evaporite. Melt inclusions from the Siberian Traps provide insight into the potential total volatile budget throughout the evolution of the large igneous province. These droplets of trapped melt may preserve volatile species that would otherwise have degassed at the time of eruption. We present data from the analysis of more than 100 melt inclusions, including both homogenized inclusions and rare glassy inclusions with low crystallinity. Many melt inclusions from tuffs and flows near the base of the Siberian Traps sequence are substantially enriched in chlorine and fluorine compared to Deccan Traps and Laki melt inclusions (Self et al., 2008; Thordarson et al., 1996). These inclusions record chlorine concentrations up to ~1400 ppm, and fluorine concentrations up to ~5000 ppm. Olivines from the Maymechinsky suite, recognized as the last extrusive products of Siberian Traps volcanism, contain melt inclusions with maximum sulfur concentrations in the range of ~5000 ppm and substantial concentrations of chlorine. Intrusive igneous rocks from the province also display significant volatile contents. A sill from the Ust-Ilimsk region yielded plagioclase-hosted melt inclusions which contain chlorine and fluorine concentrations in the range of one weight percent. Visscher et al. (2004) proposed that chlorofluorocarbon compounds (CFCs) may have played a major role in the terrestrial end-Permian extinction. These CFCs are powerful catalysts for the breakdown of ozone, a process which can expose the biosphere to increased ultraviolet radiation. Measurements of elevated chlorine and fluorine from the Siberian Traps may thus provide a concrete source for CFCs that could have triggered this kill mechanism.

Relative effects on global warming of halogenated methanes and ethanes of social and industrial interest

NASA Technical Reports Server (NTRS)

Fisher, Donald A.; Hales, Charles H.; Wang, Wei-Chyung; Ko, Malcolm K. W.; Sze, N. Dak

1990-01-01

The relative potential global warming effects for several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; and hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a; carbon tetrachloride; and methyl chloroform) were calculated by two atmospheric modeling groups. These calculations were based on atmospheric chemistry and radiative convective models to determine the chemical profiles and the radiative processes. The resulting relative greenhouse warming when normalized to the effect of CFC-11 agree reasonably well as long as we account for differences between modeled lifetimes. Differences among results are discussed. Sensitivity of relative warming values is determined with respect to trace gas levels assumed. Transient relative global warming effects are analyzed.

Satellite observations of stratospheric hydrogen fluoride and comparisons with SLIMCAT calculations

NASA Astrophysics Data System (ADS)

Harrison, Jeremy J.; Chipperfield, Martyn P.; Boone, Christopher D.; Dhomse, Sandip S.; Bernath, Peter F.; Froidevaux, Lucien; Anderson, John; Russell, James, III

2016-08-01

The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of hydrogen fluoride (HF), the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing instruments ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer), which has been recording atmospheric spectra since 2004, and HALOE (HALogen Occultation Experiment), which recorded atmospheric spectra between 1991 and 2005, with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the agreement between observation and model is good, although the ACE-FTS measurements are biased high by ˜ 10 % relative to HALOE. The observed global HF trends reveal a substantial slowing down in the rate of increase of HF since the 1990s: 4.97 ± 0.12 % year-1 (1991-1997; HALOE), 1.12 ± 0.08 % year-1 (1998-2005; HALOE), and 0.52 ± 0.03 % year-1 (2004-2012; ACE-FTS). In comparison, SLIMCAT calculates trends of 4.01, 1.10, and 0.48 % year-1, respectively, for the same periods; the agreement is very good for all but the earlier of the two HALOE periods. Furthermore, the observations reveal variations in the HF trends with latitude and altitude; for example, between 2004 and 2012 HF actually decreased in the Southern Hemisphere below ˜ 35 km. An additional SLIMCAT simulation with repeating meteorology for the year 2000 produces much cleaner trends in HF with minimal variations with latitude and altitude. Therefore, the variations with latitude and altitude in the observed HF trends are due to variability in stratospheric dynamics on the timescale of a few years. Overall, the agreement between observation and model points towards the ongoing success of the Montreal Protocol and the usefulness of HF as a metric for stratospheric fluorine.

Groundwater studies using isotopes and noble gases as a tracer: Review and prospect

NASA Astrophysics Data System (ADS)

Kazahaya, Kohei; Yasuhara, Masaya; Takahashi, Hiroshi A.; Morikawa, Noritoshi; Ohwada, Michiko; Tosaki, Yuki; Asai, Kazuyoshi

Environmental tracers become a common tool for the groundwater study and a number of methods have been presented in order to understand groundwater flow processes, water budget, origins, chemical reaction processes and retention time. Tracers often used are selected and reviewed for their various methods and advantages as follows; 1) stable 18O, D in water, 2) stable 13C and radioactive 14C in DIC, 3) noble gases such as He, Ne, Ar, Kr, Xe and their isotopes, 4) radioactive 36Cl in dissolved chloride and some heavier isotopes, and 5) inert gaseous species such as CFCs. If they are less reactive species, they likely preserve information at the time of recharge or their origin. Use of D, 18O and the d-value of water is the powerful tool to determine the recharge area because recharged meteoric water have their inherent isotopic ratios correlated with the recharge elevation, distance from the coast, or the local topography. Carbon-bearing species are more reactive though, use of stable isotopes of DIC leads to identify its origin and helps to analyze the chemical reaction between minerals and water or gas addition processes during the groundwater flow in aquifers. Radioactive 14C has been used to estimate groundwater age however special attention should be paid for, i.e., the origin of DIC, before applying the method. Noble gas tracers are the useful species to presume recharge temperature from their concentrations in water using their temperature dependence of solubilities. Radiogenic 4He concentration can be used for the very long-term groundwater dating since the 4He is produced in the crust and is accumulated in the deep aquifers, if the local accumulation rate of 4He is known. Radioactive 36Cl has been used to determine the age of very old saline waters up to million years. This isotope will also be convenient for the dating of very younger waters, by the use of bomb-produced 36Cl resulted from surface nuclear experiments near the seawater in the 1950s. Chlorofluorocarbons (CFCs) are the gas species produced by the recent human activity and dissolve in water during the recharge, therefore, the affected younger groundwater will have equivalent CFCs concentrations with the atmospheric CFCs concentrations at the time of the recharge. As these species are easy to detect with very high sensitivity, this tracer has now been applied not only for the age determination but for the mixing or contamination of shallow young water to a deep old groundwater. As an individual method listed above is valid only for the very simple flow system, appropriate assumptions or coupling of using different tracers is necessary to understand natural complex groundwater flow system where mixing of groundwaters of different origin or age occurs. Combination of tracers helps us simulating the complex system in detail and is being a growing trend in groundwater study.

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.

Green Solvents for Precision Cleaning

NASA Technical Reports Server (NTRS)

Grandelli, Heather; Maloney, Phillip; DeVor, Robert; Surma, Jan; Hintze, Paul

2013-01-01

Aerospace machinery used in liquid oxygen (LOX) fuel systems must be precision cleaned to achieve a very low level of non-volatile residue (< 1 mg0.1 m2), especially flammable residue. Traditionally chlorofluorocarbons (CFCs) have been used in the precision cleaning of LOX systems, specifically CFC 113 (C2Cl3F3). CFCs have been known to cause the depletion of ozone and in 1987, were banned by the Montreal Protocol due to health, safety and environmental concerns. This has now led to the development of new processes in the precision cleaning of aerospace components. An ideal solvent-replacement is non-flammable, environmentally benign, non-corrosive, inexpensive, effective and evaporates completely, leaving no residue. Highlighted is a green precision cleaning process, which is contaminant removal using supercritical carbon dioxide as the environmentally benign solvent. In this process, the contaminant is dissolved in carbon dioxide, and the parts are recovered at the end of the cleaning process completely dry and ready for use. Typical contaminants of aerospace components include hydrocarbon greases, hydraulic fluids, silicone fluids and greases, fluorocarbon fluids and greases and fingerprint oil. Metallic aerospace components range from small nuts and bolts to much larger parts, such as butterfly valves 18 in diameter. A fluorinated grease, Krytox, is investigated as a model contaminant in these preliminary studies, and aluminum coupons are employed as a model aerospace component. Preliminary studies are presented in which the experimental parameters are optimized for removal of Krytox from aluminum coupons in a stirred-batch process. The experimental conditions investigated are temperature, pressure, exposure time and impeller speed. Temperatures of 308 - 423 K, pressures in the range of 8.3 - 41.4 MPa, exposure times between 5 - 60 min and impeller speeds of 0 - 1000 rpm were investigated. Preliminary results showed up to 86 cleaning efficiency with the moderate processing conditions of 323 K, 13.8 MPa, 30 min and 750 rpm.

Final report on CCQM-P151: Halocarbons in dry whole air

NASA Astrophysics Data System (ADS)

Rhoderick, George; Guenther, Franklin; Duewer, David; Lee, Jeongsoon; Seog Kim, Jin; Hall, Bradley; Weiss, Ray; Harth, Christina; Reimann, Stefan; Vollmer, Martin

2014-01-01

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a pilot study between National Metrology Institutes and atmospheric research laboratories for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2-trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM.

Developing an in vitro understanding of patient experience with hydrofluoroalkane-metered dose inhalers.

PubMed

Doub, William H; Shah, Vibhakar; Limb, Susan; Guo, Changning; Liu, Xiaofei; Ngo, Diem

2014-11-01

As a result of the Montreal Protocol on Substances that Deplete the Ozone Layer, manufacturers of metered dose inhalers began reformulating their products to use hydrofluoroalkanes (HFAs) as propellants in place of chlorofluorocarbons (CFCs). Although the new products are considered safe and efficacious by the US Food and Drug Administration (FDA), a large number of complaints have been registered via the FDA's Adverse Events Reporting System (FAERS)-more than 7000 as of May 2013. To develop a better understanding of the measurable parameters that may, in part, determine in vitro performance and thus patient compliance, we compared several CFC- and HFA-based products with respect to their aerodynamic performance in response to changes in actuator cleaning interval and interactuation delay interval. Comparison metrics examined in this study were: total drug delivered ex-actuator, fine particle dose (<5 μm), mass median aerodynamic diameter, plume width, plume temperature, plume impaction force, and actuator orifice diameter. Overall, no single metric or test condition distinguishes HFA products from CFC products, but, for individual products tested, there were a combination of metrics that differentiated one from another. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Effect of Bearing Cleaning on Long Term Bearing Life

NASA Technical Reports Server (NTRS)

Jett, Timothy Raymond; Thom, Robert L.

1998-01-01

For many years chlorofluorocarbon (CFC ) based solvents, such as Freon and 1,1,1, Trichloroethane (TCA), were used as bearing cleaning solvents for space mechanisms. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change to new ODC-free cleaners for the precision bearing cleaning. With this change the question arises what effect if any do these new cleaners have on long term bearing life. The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0* 10(exp -6) torr) at a temperature of 90C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition the bearings were visually examined and analyzed using an optical microscope.

Effect of Bearing Cleaning on Long Term Bearing Life

NASA Technical Reports Server (NTRS)

Jett, Tim; Thom, R. L.

1999-01-01

For many years chlorofluorocarbon (CFC) based solvents, such as CFC-113 and 1,1,1, trichloroethane (TCA), were used as bearing cleaning solvents for space mechanism bearings. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change requiring the use of ODC-free cleaners for precision bearing cleaning. With this change the question arises; what effect if any do these new cleaners have on long term bearing life? The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0 x 10(exp -6) torr) at a temperature of 90 C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing, the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition, the bearings were visually examined and analyzed using an optical microscope.

Correlation of refrigerant mass flow rate through adiabatic capillary tubes using mixture refrigerant carbondioxide and ethane for low temperature applications

NASA Astrophysics Data System (ADS)

Nasruddin, Syaka, Darwin R. B.; Alhamid, M. Idrus

2012-06-01

Various binary mixtures of carbon dioxide and hydrocarbons, especially propane or ethane, as alternative natural refrigerants to Chlorofluorocarbons (CFCs) or Hydro fluorocarbons (HFCs) are presented in this paper. Their environmental performance is friendly, with an ozone depletion potential (ODP) of zero and Global-warming potential (GWP) smaller than 20. The capillary tube performance for the alternative refrigerant HFC HCand mixed refrigerants have been widely studied. However, studies that discuss the performance of the capillary tube to a mixture of natural refrigerants, in particular a mixture of azeotrope carbon dioxide and ethane is still undeveloped. A method of empirical correlation to determine the mass flow rate and pipe length has an important role in the design of the capillary tube for industrial refrigeration. Based on the variables that effect the rate of mass flow of refrigerant in the capillary tube, the Buckingham Pi theorem formulated eight non-dimensional parameters to be developed into an empirical equations correlation. Furthermore, non-linear regression analysis used to determine the co-efficiency and exponent of this empirical correlation based on experimental verification of the results database.

Change in ozone trends at southern high latitudes

NASA Technical Reports Server (NTRS)

Yang, E.-S.; Cunnold, D. M.; Newchurch, M. J.; Salawitch, R. J.

2005-01-01

Long-term ozone variations at 60-70degS in spring are investigated using ground-based and satellite measurements. Strong positive correlation is shown between year-to-year variations of ozone and temperature in the Antarctic collar region in Septembers and Octobers. Based on this relationship, the effect of year-to-year variations in vortex dynamics has been filtered out. This process results in an ozone time series that shows increasing springtime ozone losses over the Antarctic until the mid-1990s. Since approximately 1997 the ozone losses have leveled off. The analysis confirms that this change is consistent across all instruments and is statistically significant at the 95% confidence level. This analysis quantifies the beginning of the recovery of the ozone hole, which is expected from the leveling off of stratospheric halogen loading due to the ban on CFCs and other halocarbons initiated by the Montreal Protocol.

Estimated emissions of chlorofluorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons based on an interspecies correlation method in the Pearl River Delta region, China.

PubMed

Wu, Jing; Fang, Xuekun; Martin, Jonathan W; Zhai, Zihan; Su, Shenshen; Hu, Xia; Han, Jiarui; Lu, Sihua; Wang, Chen; Zhang, Jianbo; Hu, Jianxin

2014-02-01

Although many studies have been conducted in recent years on the emissions of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) at the large regional (such as East Asia) and national scales, relatively few studies have been conducted for cities or metropolitan areas. In this study, 192 air samples were collected in the Pearl River Delta (PRD) region of China in November 2010. The atmospheric mixing ratios of six halocarbons were analyzed, including trichlorofluoromethane (CFC-11, CCl3F), dichlorodifluoromethane (CFC-12, CCl2F2), monochlorodifluoromethane (HCFC-22, CHClF2), 1,1-dichloro-1-fluoroethane (HCFC-141b, CH3CCl2F), 1-dichloro-1,1-fluoroethane (HCFC-142b, CH3CClF2), and 1,1,1,2-tetrafluoroethane (HFC-134a, CH2FCF3), and their emissions were estimated based on an interspecies correlation method using HCFC-22 as the reference species. The results showed no significant change in the regional concentration and emission of CFC in the past 10years, suggesting that the continuous regional emission of CFC has had no significant effect on the CFC regional concentration in the PRD region. Concentrations and emissions of HCFCs and HFCs are significantly higher compared to previous research in the PRD region (P<0.05). The largest emission was for HCFC-22, most likely due to its substitution for CFC-12 in the industrial and commercial refrigeration subsector, and the rapid development of the room air-conditioner and extruded polystyrene subsectors. The PRD's ODP-weighted emissions of the target HCFCs provided 9% (7-12%) of the national emissions for the corresponding species. The PRD's GWP-weighted emissions of the target HCFCs and HFC-134a account for 10% (7-12%) and 8% (7-9%), respectively, of the national emissions for the corresponding species, and thus are important contributions to China's total emissions. © 2013 Elsevier B.V. All rights reserved.

Metabolism of chlorofluorocarbons and polybrominated compounds by Pseudomonas putida G786(pHG-2) via an engineered metabolic pathway.

PubMed Central

Hur, H G; Sadowsky, M J; Wackett, L P

1994-01-01

The recombinant bacterium Pseudomonas putida G786(pHG-2) metabolizes pentachloroethane to glyoxylate and carbon dioxide, using cytochrome P-450CAM and toluene dioxygenase to catalyze consecutive reductive and oxidative dehalogenation reactions (L.P. Wackett, M.J. Sadowsky, L.N. Newman, H.-G. Hur, and S. Li, Nature [London] 368:627-629, 1994). The present study investigated metabolism of brominated and chlorofluorocarbon compounds by the recombinant strain. Under anaerobic conditions, P. putida G786(pHG-2) reduced 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,2-dichloroethane, and 1,1,1,2-tetrachloro-2,2-difluoroethane to products bearing fewer halogen substituents. Under aerobic conditions, P. putida G786(pHG-2) oxidized cis- and trans-1,2-dibromoethenes, 1,1-dichloro-2,2-difluoroethene, and 1,2-dichloro-1-fluoroethene. Several compounds were metabolized by sequential reductive and oxidative reactions via the constructed metabolic pathway. For example, 1,1,2,2-tetrabromoethane was reduced by cytochrome P-450CAM to 1,2-dibromoethenes, which were subsequently oxidized by toluene dioxygenase. The same pathway metabolized 1,1,1,2-tetrachloro-2,2-difluoroethane to oxalic acid as one of the final products. The results obtained in this study indicate that P. putida G786(pHG-2) metabolizes polyfluorinated, chlorinated, and brominated compounds and further demonstrates the value of using a knowledge of catabolic enzymes and recombinant DNA technology to construct useful metabolic pathways. PMID:7993096

Metabolism of chlorofluorocarbons and polybrominated compounds by Pseudomonas putida G786(pHG-2) via an engineered metabolic pathway.

PubMed

Hur, H G; Sadowsky, M J; Wackett, L P

1994-11-01

The recombinant bacterium Pseudomonas putida G786(pHG-2) metabolizes pentachloroethane to glyoxylate and carbon dioxide, using cytochrome P-450CAM and toluene dioxygenase to catalyze consecutive reductive and oxidative dehalogenation reactions (L.P. Wackett, M.J. Sadowsky, L.N. Newman, H.-G. Hur, and S. Li, Nature [London] 368:627-629, 1994). The present study investigated metabolism of brominated and chlorofluorocarbon compounds by the recombinant strain. Under anaerobic conditions, P. putida G786(pHG-2) reduced 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,2-dichloroethane, and 1,1,1,2-tetrachloro-2,2-difluoroethane to products bearing fewer halogen substituents. Under aerobic conditions, P. putida G786(pHG-2) oxidized cis- and trans-1,2-dibromoethenes, 1,1-dichloro-2,2-difluoroethene, and 1,2-dichloro-1-fluoroethene. Several compounds were metabolized by sequential reductive and oxidative reactions via the constructed metabolic pathway. For example, 1,1,2,2-tetrabromoethane was reduced by cytochrome P-450CAM to 1,2-dibromoethenes, which were subsequently oxidized by toluene dioxygenase. The same pathway metabolized 1,1,1,2-tetrachloro-2,2-difluoroethane to oxalic acid as one of the final products. The results obtained in this study indicate that P. putida G786(pHG-2) metabolizes polyfluorinated, chlorinated, and brominated compounds and further demonstrates the value of using a knowledge of catabolic enzymes and recombinant DNA technology to construct useful metabolic pathways.

Flow of river water into a karstic limestone aquifer - 2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Drenkard, S.; Schlosser, P.; Ekwurzel, B.; Weppernig, R.; McConnell, J.B.; Michel, R.L.

1998-01-01

Tritium/helium-3 (3H/3He) and chlorofluorocarbon (CFCs, CFC-11, CFC-12, CFC-113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The 3H/3He age is independent of the extent of dilution with older (3H-free and 3He(trit)-free) water. The groundwater mixtures are designated as Type-I for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl- and ??18O data for water from the Upper Floridan aquifer at Valdosta, Georgia The chlorofluorocarbons CFC-11 and CFC-113 are removed by microbial degradation and/or sorption processes in most allaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-I water. CFC-12 persists in both SO4-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg-1) permitted CFC-11 and CFC-12 dating of the fraction of regional infiltration water in Type-I mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water sam pies obtained from the Upper Floridan aquifer have CFC-12-based ages of the young traction that are consistent with the 3H concentration of the groundwater. Because of uncertainties associated with very low 3H and 3He content in dilute mixtures, 3H/3He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10??? river water. Of the 41 water samples measured for 3H/3He dating, dilution of H and low -He concentration limited 3H/3He dating to 16 mixtures in which 3H/3He ages are defined with errors ranging from ??2 to ??7.5 a (1 ??). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC-12 ages agree with 3H/3He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures Tritium data and dating based on both CFC-11 and CFC-12 in Type-I mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and 3H/3He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.

Cleaning of printed circuit assemblies with surface-mounted components

NASA Astrophysics Data System (ADS)

Arzigian, J. S.

The need for ever-increasing miniaturization of airborne instrumentation through the use of surface mounted components closely placed on printed circuit boards highlights problems with traditional board cleaning methods. The reliability of assemblies which have been cleaned with vapor degreasing and spray cleaning can be seriously compromised by residual contaminants leading to solder joint failure, board corrosion, and even electrical failure of the mounted parts. In addition, recent government actions to eliminate fully halogenated chlorofluorocarbons (CFC) and chlorinated hydrocarbons from the industrial environment require the development of new cleaning materials and techniques. This paper discusses alternative cleaning materials and techniques and results that can be expected with them. Particular emphasis is placed on problems related to surface-mounted parts. These new techniques may lead to improved circuit reliability and, at the same time, be less expensive and less environmentally hazardous than the traditional systems.

High-global warming potential F-gas emissions in California: comparison of ambient-based versus inventory-based emission estimates, and implications of refined estimates.

PubMed

Gallagher, Glenn; Zhan, Tao; Hsu, Ying-Kuang; Gupta, Pamela; Pederson, James; Croes, Bart; Blake, Donald R; Barletta, Barbara; Meinardi, Simone; Ashford, Paul; Vetter, Arnie; Saba, Sabine; Slim, Rayan; Palandre, Lionel; Clodic, Denis; Mathis, Pamela; Wagner, Mark; Forgie, Julia; Dwyer, Harry; Wolf, Katy

2014-01-21

To provide information for greenhouse gas reduction policies, the California Air Resources Board (CARB) inventories annual emissions of high-global-warming potential (GWP) fluorinated gases, the fastest growing sector of greenhouse gas (GHG) emissions globally. Baseline 2008 F-gas emissions estimates for selected chlorofluorocarbons (CFC-12), hydrochlorofluorocarbons (HCFC-22), and hydrofluorocarbons (HFC-134a) made with an inventory-based methodology were compared to emissions estimates made by ambient-based measurements. Significant discrepancies were found, with the inventory-based emissions methodology resulting in a systematic 42% under-estimation of CFC-12 emissions from older refrigeration equipment and older vehicles, and a systematic 114% overestimation of emissions for HFC-134a, a refrigerant substitute for phased-out CFCs. Initial, inventory-based estimates for all F-gas emissions had assumed that equipment is no longer in service once it reaches its average lifetime of use. Revised emission estimates using improved models for equipment age at end-of-life, inventories, and leak rates specific to California resulted in F-gas emissions estimates in closer agreement to ambient-based measurements. The discrepancies between inventory-based estimates and ambient-based measurements were reduced from -42% to -6% for CFC-12, and from +114% to +9% for HFC-134a.

A manual for a laboratory information management system (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1997-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

A manual for a Laboratory Information Management System (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1998-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

The effects of greenhouse gases on the Antarctic ozone hole in the past, present, and future

NASA Astrophysics Data System (ADS)

Newman, P. A.; Li, F.; Lait, L. R.; Oman, L.

2017-12-01

The Antarctic ozone hole is primarily caused by human-produced ozone depleting substances such as chlorine-containing chlorofluorocarbons (CFCs) and bromine-containing halons. The large ozone spring-time depletion relies on the very-cold conditions of the Antarctic lower stratosphere, and the general containment of air by the polar night jet over Antarctica. Here we show the Goddard Earth Observing System Chemistry Climate Model (GEOSCCM) coupled ocean-atmosphere-chemistry model for exploring the impact of increasing greenhouse gases (GHGs). Model simulations covering the 1960-2010 period are shown for: 1) a control ensemble with observed levels of ODSs and GHGs, 2) an ensemble with fixed 1960 GHG concentrations, and 3) an ensemble with fixed 1960 ODS levels. We look at a similar set of simulations (control, 2005 fixed GHG levels, and 2005 fixed ODS levels) with a new version of GEOSCCM over the period 2005-2100. These future simulations show that the decrease of ODSs leads to similar ozone recovery for both the control run and the fixed GHG scenarios, in spite of GHG forced changes to stratospheric ozone levels. These simulations demonstrate that GHG levels will have major impacts on the stratosphere by 2100, but have only small impacts on the Antarctic ozone hole.

Environmental tracers as indicators of karst conduits in groundwater in South Dakota, USA

USGS Publications Warehouse

Long, Andrew J.; Sawyer, J.F.; Putnam, L.D.

2008-01-01

Environmental tracers sampled from the carbonate Madison aquifer on the eastern flank of the Black Hills, South Dakota, USA indicated the approximate locations of four major karst conduits. Contamination issues are a major concern because these conduits are characterized by direct connections to sinking streams, high groundwater velocities, and proximity to public water supplies. Objectives of the study were to estimate approximate conduit locations and assess possible anthropogenic influences associated with conduits. Anomalies of young groundwater based on chlorofluorocarbons (CFCs), tritium, and electrical conductivity (EC) indicated fast moving, focused flow and thus the likely presence of conduits. ??18O was useful for determining sources of recharge for each conduit, and nitrate was a useful tracer for assessing flow paths for anthropogenic influences. Two of the four conduits terminate at or near a large spring complex. CFC apparent ages ranged from 15 years near conduits to >50 years in other areas. Nitrate-N concentrations >0.4 mg/L in groundwater were associated with each of the four conduits compared with concentrations ranging from <0.1 to 0.4 mg/L in other areas. These higher nitrate-N concentrations probably do not result from sinking streams but rather from other areas of infiltration. ?? Springer-Verlag 2007.

Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

NASA Technical Reports Server (NTRS)

Zellner, Reinhard

1990-01-01

The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

21 CFR 173.342 - Chlorofluorocarbon 113 and perfluorohexane.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Chlorofluorocarbon 113 and perfluorohexane. 173... Additives § 173.342 Chlorofluorocarbon 113 and perfluorohexane. A mixture of 99 percent chlorofluorocarbon... 113 and FC 113) and 1 percent perfluorohexane (CAS Reg. No. 355-42-0) may be safely used in accordance...

The temporal and spatial variability of halogenated trace gases in the upper troposphere.

NASA Astrophysics Data System (ADS)

Oram, D.; O'Sullivan, D.; Brenninkmeijer, C.; van Velthoven, P.; Sturges, W.

2007-12-01

Halogenated trace gases play an important role in stratospheric and tropospheric chemistry, particularly affecting ozone concentrations. In addition they have direct and indirect effects on radiative forcing, and impact on tropospheric reactivity. Data from the CARIBIC project (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrumented Container) have been used in conjunction with back-trajectory analysis to further our understanding of the chemical composition, inter-hemispheric distribution and source regions of halogenated compounds in the upper troposphere and lower stratosphere. Whole air samples collected within CARIBIC, have been analyzed using gas chromatography mass spectrometry for around 35 halocarbons and related trace gases, among them many potent greenhouse gases and species important for ozone depletion. The large spatial and temporal coverage of the CARIBIC project has enabled new work to be done investigating recent inter-annual trends in the CFCs, halons, and other anthropogenic halocarbons, as well as identifying clear inter-hemispheric and seasonal variability for a number of species, such as methylene chloride, HCFCs, methyl chloride, methyl bromide, methyl iodide and several reactive short lived bromo and chloro carbons. In this paper results from the CARIBIC flights to China and the Philippines will be highlighted, to discuss anthropogenic emissions of ozone depleting and greenhouse gases, from Asia and Africa. Data from flights to South America will also be presented. As production and consumption of many of these substances are being phased out in Europe and North America, emissions from Asia, Africa and also South America are becoming increasingly more important. Emissions from these regions are also of interest, as the most significant sources are often collocated with regions of convection in the tropics and sub-tropics. Thus enabling a greater proportion of the substances emitted to reach the stratosphere, where they have the largest impact on ozone.

Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions

USGS Publications Warehouse

Sebol, L.A.; Robertson, W.D.; Busenberg, E.; Plummer, Niel; Ryan, M.C.; Schiff, S.L.

2007-01-01

A detailed local-scale monitoring network was used to assess CFC distribution in an unconfined sand aquifer in southwestern Ontario where the zone of 1-5-year-old groundwater was known with certainty because of prior use of a bromide tracer. Groundwater ???5 years old was confined to an aerobic zone at ???5 m depth and had CFC concentrations consistent with modern atmospheric mixing ratios at recharge temperatures of 7-11 ??C, as was observed in the 3-m thick vadose zone at the site. At depths below 6 m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6-7 m depth, and a Mn and Fe reducing zone below 7 m depth. In the anaerobic zone, 3H/3He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13 m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3H/3He ages. Noble gas data indicated that the apparent CFC mass loss was not likely the result of gas stripping from possible bubble formation; thus, CFC degradation was indicated in the anoxic zone. The field data are consistent with first-order degradation rates of 0.3 yr-1 for CFC-12, 0.7 yr-1 for CFC-11, and 1.6 yr-1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO3 and dissolved oxygen (DO). Similar behavior has been observed at other sites [Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrification in an agricultural watershed: electron and mass balance along groundwater flow path. Water Resour. Res. 36 (6), 1545-1559; Hinsby, K., Hojberg, A.L., Engesgaard, P., Jensen, K.H., Larsen, F., Plummer, L.N., Busenberg, E., Accepted for publication. Transport and degradation of chlorofluorocarbons (CFCs) in a pyritic aquifer, Rabis Creek, Denmark. Water Resour. Res.], further demonstrating that the use of CFCs for age-dating anaerobic groundwater should be approached with caution, particularly if the sediment contains pyrite. ?? 2007 Elsevier B.V. All rights reserved.

Reliability of the Dutch-language version of the Communication Function Classification System and its association with language comprehension and method of communication.

PubMed

Vander Zwart, Karlijn E; Geytenbeek, Joke J; de Kleijn, Maaike; Oostrom, Kim J; Gorter, Jan Willem; Hidecker, Mary Jo Cooley; Vermeulen, R Jeroen

2016-02-01

The aims of this study were to determine the intra- and interrater reliability of the Dutch-language version of the Communication Function Classification System (CFCS-NL) and to investigate the association between the CFCS level and (1) spoken language comprehension and (2) preferred method of communication in children with cerebral palsy (CP). Participants were 93 children with CP (50 males, 43 females; mean age 7y, SD 2y 6mo, range 2y 9mo-12y 10mo; unilateral spastic [n=22], bilateral spastic [n=51], dyskinetic [n=15], ataxic [n=3], not specified [n=2]; Gross Motor Function Classification System level I [n=16], II [n=14], III, [n=7], IV [n=24], V [n=31], unknown [n=1]), recruited from rehabilitation centres throughout the Netherlands. Because some centres only contributed to part of the study, different numbers of participants are presented for different aspects of the study. Parents and speech and language therapists (SLTs) classified the communication level using the CFCS. Kappa was used to determine the intra- and interrater reliability. Spearman's correlation coefficient was used to determine the association between CFCS level and spoken language comprehension, and Fisher's exact test was used to examine the association between the CFCS level and method of communication. Interrater reliability of the CFCS-NL between parents and SLTs was fair (r=0.54), between SLTs good (r=0.78), and the intrarater (SLT) reliability very good (r=0.85). The association between the CFCS and spoken language comprehension was strong for SLTs (r=0.63) and moderate for parents (r=0.51). There was a statistically significant difference between the CFCS level and the preferred method of communication of the child (p<0.01). Also, CFCS level classification showed a statistically significant difference between parents and SLTs (p<0.01). These data suggest that the CFCS-NL is a valid and reliable clinical tool to classify everyday communication in children with CP. Preferably, professionals should classify the child's CFCS level in collaboration with the parents to acquire the most comprehensive information about the everyday communication of the child in various situations both with familiar and with unfamiliar partners. © 2015 Mac Keith Press.

Montreal Protocol: The Gift that Keeps on Giving

NASA Astrophysics Data System (ADS)

Reifsnyder, D. A.

2012-12-01

Unlike many of my contemporaries, I did not begin my career with CFCs, ozone, and the Montreal Protocol. Instead, I began with climate change issue. In October 1989 I became Director of the Department of State's Office of Global Change, after the George H.W. Bush Administration agreed to host the Third Plenary of the Intergovernmental Panel on Climate Change (IPCC) at Georgetown University. Bert Bolin was IPCC Chair, Bill Reilly was EPA Administrator and John Sununu was White House Chief of Staff. I survived those early years and afterward had a long run with the climate change policy - lasting through six administrations. Last year I even chaired the Ad Hoc Group on Long-Term Cooperative Action in Durban at the 17th Conference of the Parties under the UN FCCC. I really plunged into the ozone issue in 2006 when I became the Deputy Assistant Secretary for Environment. By then ozone was hardly ever mentioned, except to recall that the Montreal Protocol was undoubtedly the most successful multilateral environmental agreement ever undertaken - and to contrast it nostalgically with others that have not fared so well - particularly climate. Even worse, ozone was ancient history and most people thought we had solved that problem. Richard Benedict's Ozone Diplomacy had long been a staple of college courses on the global environment but few graduates saw a career in ozone, and it had become difficult to find people in government who were willing to work on it. In early 2007, my staff and I met with colleagues at EPA to brainstorm about the global effort to phase out chlorofluorocarbons (CFCs) and move to alternatives - hydrochlorofluorocarbons (HCFCs). The transition from CFCs was nearing its end but HCFCs, though less potent, were still a problem for the ozone layer. We began to wonder -- could something be done to accelerate the phaseouts of HCFCs? We realized that proposing an acceleration would mean that developed countries would need to go first. Only later would they be followed by developing countries. The question was, could we do it? And if we could, how could we get others developed countries and then developing countries on side? After our internal discussions, State and EPA convened a workshop with U.S. stakeholders from the private sector and the environmental community. To our delight, both groups thought the United States should take the initiative. In retrospect, the winds were favorable - 2007 marked the 25th Anniversary of the Montreal Protocol and many wanted to celebrate it with something significant. The private sector felt that it could meet an accelerated timetable for phasing out HCFCs - the technology was there. It was also clear that money in the Montreal Protocol Multilateral Fund had begun to decline with the developing country phaseout of CFCs and would decline even more steeply unless a new basis were found to continue it. But favorable winds do not always make for a smooth sail - and path to the accelerated phaseouts of 2007 proved challenging. At the time, practically no one thought the effort would succeed. Still, we did succeed. Yet even then it took time to for many to appreciate the significant benefits for the climate system, beyond the benefits to the stratospheric ozone layer. In fact, the continuing story of the Montreal Protocol is one of the gift that keeps on giving.

21 CFR 700.23 - Chlorofluorocarbon propellants.

Code of Federal Regulations, 2010 CFR

2010-04-01

...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.23 Chlorofluorocarbon propellants. The use of chlorofluorocarbons in cosmetics as propellants in self-pressurized containers is prohibited as...

21 CFR 700.23 - Chlorofluorocarbon propellants.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.23 Chlorofluorocarbon propellants. The use of chlorofluorocarbons in cosmetics as propellants in self-pressurized containers is prohibited as...

21 CFR 700.23 - Chlorofluorocarbon propellants.

Code of Federal Regulations, 2014 CFR

2014-04-01

...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.23 Chlorofluorocarbon propellants. The use of chlorofluorocarbons in cosmetics as propellants in self-pressurized containers is prohibited as...

21 CFR 700.23 - Chlorofluorocarbon propellants.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.23 Chlorofluorocarbon propellants. The use of chlorofluorocarbons in cosmetics as propellants in self-pressurized containers is prohibited as...

21 CFR 700.23 - Chlorofluorocarbon propellants.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.23 Chlorofluorocarbon propellants. The use of chlorofluorocarbons in cosmetics as propellants in self-pressurized containers is prohibited as...

Mobilization of primitive and committed hematopoietic progenitors in nonhuman primates treated with defibrotide and recombinant human granulocyte colony-stimulating factor.

PubMed

Carlo-Stella, Carmelo; Di Nicola, Massimo; Longoni, Paolo; Milani, Raffaella; Milanesi, Marco; Guidetti, Anna; Haanstra, Krista; Jonker, Margaret; Cleris, Loredana; Magni, Michele; Formelli, Franca; Gianni, Alesssandro M

2004-01-01

The aim of this study was to evaluate the capacity of defibrotide in enhancing cytokine-induced hematopoietic mobilization in rhesus monkeys. Animals received recombinant human granulocyte colony-stimulating factor (rhG-CSF, 100 microg/kg/day SC for 5 days) and, after a 4- to 6-week washout period, were remobilized with defibrotide (15 mg/kg/hour continuous intravenous for 5 days) plus rhG-CSF. Hematopoietic mobilization was evaluated by complete blood counts, differential counts, as well as frequency and absolute numbers of colony-forming cells (CFCs), high-proliferative potential CFCs (HPP-CFCs), and long-term culture-initiating cells (LTC-ICs). Compared to baseline values, rhG-CSF increased circulating CFCs, HPP-CFCs, and LTC-ICs by 158-, 125-, and 67-fold, respectively; the same figures for defibrotide/rhG-CSF were 299-, 1452-, and 295-fold, respectively. Defibrotide/rhG-CSF treatment compared to rhG-CSF alone increased CFCs, HPP-CFCs, and LTC-ICs by 1.4- (35,089 vs 25,825, p< or =0.02), 6- (4358 vs 748, p< or =0.02), and 5-fold (884 vs 168, p< or =0.04), respectively. We then evaluated the effects of a 2-day defibrotide treatment associated with a 5-day rhG-CSF treatment. Compared to rhG-CSF, defibrotide/rhG-CSF increased the mobilization of CFCs, HPP-CFCs, and LTC-ICs by 2- (31,128 vs 15,527, p< or =0.05), 8- (5361 vs 660, p< or =0.01), and 8-fold (954 vs 119, p< or =0.01), respectively. Our data demonstrate that in nonhuman primates: 1) defibrotide enhances rhG-CSF-elicited mobilization of primitive and committed progenitors; and 2) a 2-day defibrotide injection is as effective as a 5-day injection.

Non-positive autoimmune responses against CYP2E1 in refrigeration mechanics exposed to halogenated hydrocarbons.

PubMed

Gunnare, Sara; Vidali, Matteo; Lillienberg, Linnéa; Ernstgård, Lena; Sjögren, Bengt; Hagberg, Mats; Albano, Emanuele; Johanson, Gunnar

2007-09-20

The aim of the study was to determine if occupational exposure to hydrofluorocarbons (HFC) and hydrochlorofluorocarbons (HCFC) generates autoimmune responses against CYP2E1. HFCs and HCFCs have replaced the chlorofluorocarbons (CFC) in e.g. refrigeration installations and air-conditioning systems. During the substitution period, refrigeration mechanics reported symptoms like asthma, influenza-like reactions, and joint troubles. These symptoms resemble those of chronic inflammatory diseases with an autoimmune component. Since exposure to structurally similar chemicals, e.g. halothane, has previously been associated with autoimmune responses and diseases, autoimmunity among the refrigeration mechanics might hypothetically explain the reported inflammatory symptoms. Serum from 44 Swedish men, occupationally exposed to halogenated hydrocarbons, was screened for antibodies against CYP2E1 with enzyme-linked immunosorbent assay. Thirty of the workers had asthma, joint problems or influenza-like symptoms whereas 14 of them had no such symptoms. They were all selected from a cohort of 280 refrigeration mechanics. Unexposed, healthy, Swedish men (n=35) constituted control group. The study was approved by the Ethics Committee at Karolinska Institutet. No increase in autoantibodies against CYP2E1 was detected among the occupationally exposed workers as compared to the unexposed controls. Further, there was no difference in antibody titer between the exposed workers with symptoms and the exposed, asymtomatic workers or the unexposed controls. The present study does not completely exclude a connection between exposure and effect but makes the relation less likely at these exposure levels.

Developing and validating the Communication Function Classification System for individuals with cerebral palsy

PubMed Central

HIDECKER, MARY JO COOLEY; PANETH, NIGEL; ROSENBAUM, PETER L; KENT, RAYMOND D; LILLIE, JANET; EULENBERG, JOHN B; CHESTER, KEN; JOHNSON, BRENDA; MICHALSEN, LAUREN; EVATT, MORGAN; TAYLOR, KARA

2011-01-01

Aim The purpose of this study was to create and validate a Communication Function Classification System (CFCS) for children with cerebral palsy (CP) that can be used by a wide variety of individuals who are interested in CP. This paper reports the content validity, interrater reliability, and test–retest reliability of the CFCS for children with CP. Method An 11-member development team created comprehensive descriptions of the CFCS levels, and four nominal groups comprising 27 participants critiqued these levels. Within a Delphi survey, 112 participants commented on the clarity and usefulness of the CFCS. Interrater reliability was completed by 61 professionals and 68 parents/relatives who classified 69 children with CP aged 2 to 18 years. Test–retest reliability was completed by 48 professionals who allowed at least 2 weeks between classifications. The participants who assessed the CFCS were all relevant stakeholders: adults with CP, parents of children with CP, educators, occupational therapists, physical therapists, physicians, and speech–language pathologists. Results The interrater reliability of the CFCS was 0.66 between two professionals and 0.49 between a parent and a professional. Professional interrater reliability improved to 0.77 for classification of children older than 4 years. The test–retest reliability was 0.82. Interpretation The CFCS demonstrates content validity and shows very good test–retest reliability, good professional interrater reliability, and moderate parent–professional interrater reliability. Combining the CFCS with the Gross Motor Function Classification System and the Manual Ability Classification System contributes to a functional performance view of daily life for individuals with CP, in accordance with the World Health Organization’s International Classification of Functioning, Disability and Health. PMID:21707596

Groundwater flow system under a rapidly urbanizing coastal city as determined by hydrogeochemistry

NASA Astrophysics Data System (ADS)

Kagabu, Makoto; Shimada, Jun; Delinom, Robert; Tsujimura, Maki; Taniguchi, Makoto

2011-01-01

In the Jakarta area (Indonesia), excessive groundwater pumping due to the rapidly increasing population has caused groundwater-related problems such as brackish water contamination in coastal areas and land subsidence. In this study, we adopted multiple hydrogeochemical techniques to demonstrate the groundwater flow system in the Jakarta area. Although almost all groundwater existing in the Jakarta basin is recharged at similar elevations, the water quality and residence time demonstrates a clear difference between the shallow and deep aquifers. Due to the rapid decrease in the groundwater potential in urban areas, we found that the seawater intrusion and the shallow and deep groundwaters are mixing, a conclusion confirmed by major ions, Br -:Cl - ratios, and chlorofluorocarbon (CFC)-12 analysis. Spring water and groundwater samples collected from the southern mountainside area show younger age characteristics with high concentrations of 14C and Ca-HCO 3 type water chemistry. We estimated the residence times of these groundwaters within 45 years under piston flow conditions by tritium analysis. Also, these groundwater ages can be limited to 20-30 years with piston flow evaluated by CFCs. Moreover, due to the magnitude of the CFC-12 concentration, we can use a pseudo age indicator in this field study, because we found a positive correlation between the major type of water chemistry and the CFC-12 concentration.

Nonflammable, Nonaqueous, Low Atmospheric Impact, High Performance Cleaning Solvents

NASA Technical Reports Server (NTRS)

Dhooge, P. M.; Glass, S. M.; Nimitz, J. S.

2001-01-01

For many years, chlorofluorocarbon (CFC) and chlorocarbon solvents have played an important part in aerospace operations. These solvents found extensive use as cleaning and analysis (EPA) solvents in precision and critical cleaning. However, CFCs and chlorocarbon solvents have deleterious effects on the ozone layer, are relatively strong greenhouse gases, and some are suspect or known carcinogens. Because of their ozone-depletion potential (ODP), the Montreal Protocol and its amendments, as well as other environmental regulations, have resulted in the phaseout of CFC-113 and 1,1,1-trichloroethane (TCA). Although alternatives have been recommended, they do not perform as well as the original solvents. In addition, some analyses, such as the infrared analysis of extracted hydrocarbons, cannot be performed with the substitute solvents that contain C-H bonds. CFC-113 solvent has been used for many critical aerospace applications. CFC-113, also known as Freon (registered) TF, has been used extensively in NASA's cleaning facilities for precision and critical cleaning, in particular the final rinsing in Class 100 areas, with gas chromatography analysis of rinse residue. While some cleaning can be accomplished by other processes, there are certain critical applications where CFC-113 or a similar solvent is highly cost-effective and ensures safety. Oxygen system components are one example where a solvent compatible with oxygen and capable of removing fluorocarbon grease is needed. Electronic components and precision mechanical components can also be damaged by aggressive cleaning solvents.

Analysis of the UV-B Regime and Potential Effects on Alfalfa

NASA Technical Reports Server (NTRS)

Seitz, Jeffery C.

1998-01-01

Life at the surface of the Earth, over the last 400 m.y., evolved under conditions of decreased short-wave radiation (i.e., ultraviolet) relative to solar output due to absorption and scattering by constituents (e.g., ozone, water vapor, aerosols) in the upper atmosphere. However, a significant amount of ultraviolet radiation in the range from 280-320 nm, known as ultraviolet-B radiation, reaches the Earth's surface and has sufficient energy to be damaging to biologic tissue. Natural fluctuations in atmospheric constituents (seasonal variation, volcanic eruptions, etc.), changes in the orbital attitude of the Earth (precession, axial tilt, orbital eccentricity), and long-term solar variability contribute to changes in the total amount of ultraviolet radiation reaching the surface of the Earth, and thus, the biosphere. More recently, the atmospheric release of commercial propellants and refrigerants, known as chlorofluorocarbons (CFCs), has contributed to a significant depletion in naturally occurring ozone in the stratosphere. Thus, decreased stratospheric ozone has resulted in an increased UV-B flux at the Earth's surface which may have profound effects on terrestrial and marine organisms. In this study, we are investigating the effects of differing solar UV-B fluxes on alfalfa (Medicago sativa L.), an important agricultural crop. A long-term goal of this research is to develop spectral signatures to detect plant response to increased UV-B radiation from remote sensor platforms.

Aquifer Susceptibility in Virginia: Data on Chemical and Isotopic Composition, Recharge Temperature, and Apparent Age of Water from Wells and Springs, 1998-2000

USGS Publications Warehouse

Nelms, David L.; Harlow, George E.

2003-01-01

The determination of aquifer susceptibility to contamination from near-surface sources by the use of ground-water dating techniques is a critical part of Virginia's Source Water Assessment Program. As part of the Virginia Aquifer Susceptibility study, water samples were collected between 1998 and 2000 from 145 wells and 6 springs in various hydrogeologic settings across the Commonwealth. Samples were analyzed to determine water chemistry?including nitrate (NO3), dissolved organic carbon (DOC), and radon-222 (222Rn), major dissolved and noble gases?nitrogen (N2), argon (Ar), oxygen (O2), carbon dioxide (CO2), methane (CH4), helium (He), and neon (Ne), environmental tracers?chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and tritium/helium-3 (3H/3He), carbon isotopes?carbon-14 (14C) and carbon-13 (d13C), and stable isotopes of oxygen (d18O) and hydrogen (d2H). The chemical and isotopic composition, recharge temperatures, and apparent ages of these water samples are presented in this report. Data collected between 1999 and 2000 from 18 wells in Virginia as part of two other studies by the U.S. Geological Survey also are presented. Most of the sites sampled serve as public water supplies and are included in the comprehensive Source Water Assessment Program for the Commonwealth.

Chilling Prospect: Climate Change Effects of Mismanaged Refrigerants in China.

PubMed

Duan, Huabo; Miller, T Reed; Liu, Gang; Zeng, Xianlai; Yu, Keli; Huang, Qifei; Zuo, Jian; Qin, Yufei; Li, Jinhui

2018-06-05

The global community has responded to the dual threats of ozone depletion and climate change from refrigerant emissions (e.g., chlorofluorocarbons, CFCs, and hydrofluorocarbons, HFCs) in refrigerators and air conditioners (RACs) by agreeing to phase out the production of the most damaging chemicals and replacing them with substitutes. Since these refrigerants are "banked" in products during their service life, they will continue to impact our environment for decades to come if they are released due to mismanagement at the end of life. Addressing such long-term impacts of refrigerants requires a dynamic understanding of the RACs' life cycle, which was largely overlooked in previous studies. Based on field surveys and a dynamic model, we reveal the lingering ozone depletion potential (ODP) and significant global warming potential (GWP) of scrap refrigerants in China, the world's largest producer (62%) and consumer (46%) of RACs in 2015, which comes almost entirely from air conditioners rather than refrigerators. If the use and waste management of RACs continue with the current trend, the total GWP of scrap refrigerants in China will peak by 2025 at a level of 135.2 ± 18.9 Mt CO 2 e (equal to approximately 1.2% ± 0.2% of China's total greenhouse gas emissions or the national total of either The Netherlands and Czech Republic in 2015). Our results imply an urgent need for improving the recycling and waste management of RACs in China.

Final report on international comparison CCQM-K83: Halocarbons in dry whole air

NASA Astrophysics Data System (ADS)

Rhoderick, George; Guenther, Franklin; Duewer, David; Lee, Jeongsoon; Moon, Dongmin; Lee, Jinbok; Lim, Jeongsik; Seog Kim, Jin

2014-01-01

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a key comparison for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2 trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2 tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Evidence of deep circulation in two perennially ice-covered Antarctic lakes

USGS Publications Warehouse

Tyler, S.W.; Cook, P.G.; Butt, A.Z.; Thomas, J.M.; Doran, P.T.; Lyons, W.B.

1998-01-01

The perennial ice covers found on many of the lakes in the McMurdo Dry Valley region of the Antarctic have been postulated to severely limit mixing and convective turnover of these unique lakes. In this work, we utilize chlorofluorocarbon (CFC) concentration profiles from Lakes Hoare and Fryxell in the McMurdo Dry Valley to determine the extent of deep vertical mixing occurring over the last 50 years. Near the ice-water interface, CFC concentrations in both lakes were well above saturation, in accordance with atmospheric gas supersaturations resulting from freezing under the perennial ice covers. Evidence of mixing throughout the water column at Lake Hoare was confirmed by the presence of CFCs throughout the water column and suggests vertical mixing times of 20-30 years. In Lake Fryxell, CFC-11, CFC-12, and CFC-113 were found in the upper water column; however, degradation of CFC-11 and CFC-12 in the anoxic bottom waters appears to be occurring with CFC-113 only present in these bottom waters. The presence of CFC-113 in the bottom waters, in conjunction with previous work detecting tritium in these waters, strongly argues for the presence of convective mixing in Lake Fryxell. The evidence for deep mixing in these lakes may be an important, yet overlooked, phenomenon in the limnology of perennially ice-covered lakes.

40 CFR 721.4360 - Certain hydrogen containing chlorofluorocarbons.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Certain hydrogen containing chlorofluorocarbons. 721.4360 Section 721.4360 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4360 Certain hydrogen containing chlorofluorocarbons. (a) Chemical...

40 CFR 721.4360 - Certain hydrogen containing chlorofluorocarbons.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Certain hydrogen containing chlorofluorocarbons. 721.4360 Section 721.4360 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4360 Certain hydrogen containing chlorofluorocarbons. (a) Chemical...

40 CFR 721.4360 - Certain hydrogen containing chlorofluorocarbons.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Certain hydrogen containing chlorofluorocarbons. 721.4360 Section 721.4360 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4360 Certain hydrogen containing chlorofluorocarbons. (a) Chemical...

40 CFR 721.4360 - Certain hydrogen containing chlorofluorocarbons.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Certain hydrogen containing chlorofluorocarbons. 721.4360 Section 721.4360 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4360 Certain hydrogen containing chlorofluorocarbons. (a) Chemical...

40 CFR 721.4360 - Certain hydrogen containing chlorofluorocarbons.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Certain hydrogen containing chlorofluorocarbons. 721.4360 Section 721.4360 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4360 Certain hydrogen containing chlorofluorocarbons. (a) Chemical...

Multiple giant cell lesions in patients with Noonan syndrome and cardio-facio-cutaneous syndrome.

PubMed

Neumann, Thomas E; Allanson, Judith; Kavamura, Ines; Kerr, Bronwyn; Neri, Giovanni; Noonan, Jacqueline; Cordeddu, Viviana; Gibson, Kate; Tzschach, Andreas; Krüger, Gabriele; Hoeltzenbein, Maria; Goecke, Timm O; Kehl, Hans Gerd; Albrecht, Beate; Luczak, Klaudiusz; Sasiadek, Maria M; Musante, Luciana; Laurie, Rohan; Peters, Hartmut; Tartaglia, Marco; Zenker, Martin; Kalscheuer, Vera

2009-04-01

Noonan syndrome (NS) and cardio-facio-cutaneous syndrome (CFCS) are related developmental disorders caused by mutations in genes encoding various components of the RAS-MAPK signaling cascade. NS is associated with mutations in the genes PTPN11, SOS1, RAF1, or KRAS, whereas CFCS can be caused by mutations in BRAF, MEK1, MEK2, or KRAS. The NS phenotype is rarely accompanied by multiple giant cell lesions (MGCL) of the jaw (Noonan-like/MGCL syndrome (NL/MGCLS)). PTPN11 mutations are the only genetic abnormalities reported so far in some patients with NL/MGCLS and in one individual with LEOPARD syndrome and MGCL. In a cohort of 75 NS patients previously tested negative for mutations in PTPN11 and KRAS, we detected SOS1 mutations in 11 individuals, four of whom had MGCL. To explore further the relevance of aberrant RAS-MAPK signaling in syndromic MGCL, we analyzed the established genes causing CFCS in three subjects with MGCL associated with a phenotype fitting CFCS. Mutations in BRAF or MEK1 were identified in these patients. All mutations detected in these seven patients with syndromic MGCL had previously been described in NS or CFCS without apparent MGCL. This study demonstrates that MGCL may occur in NS and CFCS with various underlying genetic alterations and no obvious genotype-phenotype correlation. This suggests that dysregulation of the RAS-MAPK pathway represents the common and basic molecular event predisposing to giant cell lesion formation in patients with NS and CFCS rather than specific mutation effects.

Multiple giant cell lesions in patients with Noonan syndrome and cardio-facio-cutaneous syndrome

PubMed Central

Neumann, Thomas E; Allanson, Judith; Kavamura, Ines; Kerr, Bronwyn; Neri, Giovanni; Noonan, Jacqueline; Cordeddu, Viviana; Gibson, Kate; Tzschach, Andreas; Krüger, Gabriele; Hoeltzenbein, Maria; Goecke, Timm O; Kehl, Hans Gerd; Albrecht, Beate; Luczak, Klaudiusz; Sasiadek, Maria M; Musante, Luciana; Laurie, Rohan; Peters, Hartmut; Tartaglia, Marco; Zenker, Martin; Kalscheuer, Vera

2009-01-01

Noonan syndrome (NS) and cardio-facio-cutaneous syndrome (CFCS) are related developmental disorders caused by mutations in genes encoding various components of the RAS-MAPK signaling cascade. NS is associated with mutations in the genes PTPN11, SOS1, RAF1, or KRAS, whereas CFCS can be caused by mutations in BRAF, MEK1, MEK2, or KRAS. The NS phenotype is rarely accompanied by multiple giant cell lesions (MGCL) of the jaw (Noonan-like/MGCL syndrome (NL/MGCLS)). PTPN11 mutations are the only genetic abnormalities reported so far in some patients with NL/MGCLS and in one individual with LEOPARD syndrome and MGCL. In a cohort of 75 NS patients previously tested negative for mutations in PTPN11 and KRAS, we detected SOS1 mutations in 11 individuals, four of whom had MGCL. To explore further the relevance of aberrant RAS-MAPK signaling in syndromic MGCL, we analyzed the established genes causing CFCS in three subjects with MGCL associated with a phenotype fitting CFCS. Mutations in BRAF or MEK1 were identified in these patients. All mutations detected in these seven patients with syndromic MGCL had previously been described in NS or CFCS without apparent MGCL. This study demonstrates that MGCL may occur in NS and CFCS with various underlying genetic alterations and no obvious genotype–phenotype correlation. This suggests that dysregulation of the RAS-MAPK pathway represents the common and basic molecular event predisposing to giant cell lesion formation in patients with NS and CFCS rather than specific mutation effects. PMID:18854871

21 CFR 173.342 - Chlorofluorocarbon 113 and perfluorohexane.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Chlorofluorocarbon 113 and perfluorohexane. 173.342... HUMAN CONSUMPTION Specific Usage Additives § 173.342 Chlorofluorocarbon 113 and perfluorohexane. A..., also known as fluorocarbon 113, CFC 113 and FC 113) and 1 percent perfluorohexane (CAS Reg. No. 355-42...

Promoting consistent use of the communication function classification system (CFCS).

PubMed

Cunningham, Barbara Jane; Rosenbaum, Peter; Hidecker, Mary Jo Cooley

2016-01-01

We developed a Knowledge Translation (KT) intervention to standardize the way speech-language pathologists working in Ontario Canada's Preschool Speech and Language Program (PSLP) used the Communication Function Classification System (CFCS). This tool was being used as part of a provincial program evaluation and standardizing its use was critical for establishing reliability and validity within the provincial dataset. Two theoretical foundations - Diffusion of Innovations and the Communication Persuasion Matrix - were used to develop and disseminate the intervention to standardize use of the CFCS among a cohort speech-language pathologists. A descriptive pre-test/post-test study was used to evaluate the intervention. Fifty-two participants completed an electronic pre-test survey, reviewed intervention materials online, and then immediately completed an electronic post-test survey. The intervention improved clinicians' understanding of how the CFCS should be used, their intentions to use the tool in the standardized way, and their abilities to make correct classifications using the tool. Findings from this work will be shared with representatives of the Ontario PSLP. The intervention may be disseminated to all speech-language pathologists working in the program. This study can be used as a model for developing and disseminating KT interventions for clinicians in paediatric rehabilitation. The Communication Function Classification System (CFCS) is a new tool that allows speech-language pathologists to classify children's skills into five meaningful levels of function. There is uncertainty and inconsistent practice in the field about the methods for using this tool. This study used combined two theoretical frameworks to develop an intervention to standardize use of the CFCS among a cohort of speech-language pathologists. The intervention effectively increased clinicians' understanding of the methods for using the CFCS, ability to make correct classifications, and intention to use the tool in the standardized way in the future.

21 CFR 201.320 - Warning statements for drug products containing or manufactured with chlorofluorocarbons or other...

Code of Federal Regulations, 2012 CFR

2012-04-01

... manufactured with chlorofluorocarbons or other ozone-depleting substances. 201.320 Section 201.320 Food and... products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances. (a)(1... harms public health and the environment by destroying ozone in the upper atmosphere. (2) The warning...

21 CFR 201.320 - Warning statements for drug products containing or manufactured with chlorofluorocarbons or other...

Code of Federal Regulations, 2014 CFR

2014-04-01

... manufactured with chlorofluorocarbons or other ozone-depleting substances. 201.320 Section 201.320 Food and... products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances. (a)(1... harms public health and the environment by destroying ozone in the upper atmosphere. (2) The warning...

21 CFR 201.320 - Warning statements for drug products containing or manufactured with chlorofluorocarbons or other...

Code of Federal Regulations, 2010 CFR

2010-04-01

... manufactured with chlorofluorocarbons or other ozone-depleting substances. 201.320 Section 201.320 Food and... products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances. (a)(1... harms public health and the environment by destroying ozone in the upper atmosphere. (2) The warning...

21 CFR 201.320 - Warning statements for drug products containing or manufactured with chlorofluorocarbons or other...

Code of Federal Regulations, 2013 CFR

2013-04-01

... manufactured with chlorofluorocarbons or other ozone-depleting substances. 201.320 Section 201.320 Food and... products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances. (a)(1... harms public health and the environment by destroying ozone in the upper atmosphere. (2) The warning...

21 CFR 201.320 - Warning statements for drug products containing or manufactured with chlorofluorocarbons or other...

Code of Federal Regulations, 2011 CFR

2011-04-01

... manufactured with chlorofluorocarbons or other ozone-depleting substances. 201.320 Section 201.320 Food and... products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances. (a)(1... harms public health and the environment by destroying ozone in the upper atmosphere. (2) The warning...

21 CFR 173.342 - Chlorofluorocarbon 113 and perfluorohexane.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Chlorofluorocarbon 113 and perfluorohexane. 173... perfluorohexane. A mixture of 99 percent chlorofluorocarbon 113 (1,1,2-trichloro-1,2,2-trifluoroethane) (CAS Reg. No. 76-13-1, also known as fluorocarbon 113, CFC 113 and FC 113) and 1 percent perfluorohexane (CAS...

21 CFR 173.342 - Chlorofluorocarbon 113 and perfluorohexane.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Chlorofluorocarbon 113 and perfluorohexane. 173... perfluorohexane. A mixture of 99 percent chlorofluorocarbon 113 (1,1,2-trichloro-1,2,2-trifluoroethane) (CAS Reg. No. 76-13-1, also known as fluorocarbon 113, CFC 113 and FC 113) and 1 percent perfluorohexane (CAS...

21 CFR 173.342 - Chlorofluorocarbon 113 and perfluorohexane.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Chlorofluorocarbon 113 and perfluorohexane. 173... perfluorohexane. A mixture of 99 percent chlorofluorocarbon 113 (1,1,2-trichloro-1,2,2-trifluoroethane) (CAS Reg. No. 76-13-1, also known as fluorocarbon 113, CFC 113 and FC 113) and 1 percent perfluorohexane (CAS...

21 CFR 701.30 - Ingredient names established for cosmetic ingredient labeling.

Code of Federal Regulations, 2010 CFR

2010-04-01

... names for the purpose of cosmetic ingredient labeling pursuant to paragraph (e) of § 701.3: Chemical... Chlorofluorocarbon 11. Trichlorofluoromethane and 0.3 pct nitromethane CCl3F+CH3NO2 Chlorofluorocarbon 11 S. Dichlorodifluoromethane CCl2F2 Chlorofluorocarbon 12. Chlorodifluoromethane CHClF2 Hydrochlorofluorocarbon 22. 1, 2...

21 CFR 701.30 - Ingredient names established for cosmetic ingredient labeling.

Code of Federal Regulations, 2012 CFR

2012-04-01

... names for the purpose of cosmetic ingredient labeling pursuant to paragraph (e) of § 701.3: Chemical... Chlorofluorocarbon 11. Trichlorofluoromethane and 0.3 pct nitromethane CCl3F+CH3NO2 Chlorofluorocarbon 11 S. Dichlorodifluoromethane CCl2F2 Chlorofluorocarbon 12. Chlorodifluoromethane CHClF2 Hydrochlorofluorocarbon 22. 1, 2...

21 CFR 701.30 - Ingredient names established for cosmetic ingredient labeling.

Code of Federal Regulations, 2014 CFR

2014-04-01

... names for the purpose of cosmetic ingredient labeling pursuant to paragraph (e) of § 701.3: Chemical... Chlorofluorocarbon 11. Trichlorofluoromethane and 0.3 pct nitromethane CCl3F+CH3NO2 Chlorofluorocarbon 11 S. Dichlorodifluoromethane CCl2F2 Chlorofluorocarbon 12. Chlorodifluoromethane CHClF2 Hydrochlorofluorocarbon 22. 1, 2...

21 CFR 701.30 - Ingredient names established for cosmetic ingredient labeling.

Code of Federal Regulations, 2011 CFR

2011-04-01

... names for the purpose of cosmetic ingredient labeling pursuant to paragraph (e) of § 701.3: Chemical... Chlorofluorocarbon 11. Trichlorofluoromethane and 0.3 pct nitromethane CCl3F+CH3NO2 Chlorofluorocarbon 11 S. Dichlorodifluoromethane CCl2F2 Chlorofluorocarbon 12. Chlorodifluoromethane CHClF2 Hydrochlorofluorocarbon 22. 1, 2...

21 CFR 701.30 - Ingredient names established for cosmetic ingredient labeling.

Code of Federal Regulations, 2013 CFR

2013-04-01

... names for the purpose of cosmetic ingredient labeling pursuant to paragraph (e) of § 701.3: Chemical... Chlorofluorocarbon 11. Trichlorofluoromethane and 0.3 pct nitromethane CCl3F+CH3NO2 Chlorofluorocarbon 11 S. Dichlorodifluoromethane CCl2F2 Chlorofluorocarbon 12. Chlorodifluoromethane CHClF2 Hydrochlorofluorocarbon 22. 1, 2...

Reply to "Comment on 'Cosmic-ray-driven reaction and greenhouse effect of halogenated molecules: Culprits for atmospheric ozone depletion and global climate change' by Rolf Müller and Jens-Uwe Grooß"

NASA Astrophysics Data System (ADS)

Lu, Q.-B.

2014-04-01

In their Comment, Müller and Grooß continuously use problematic "observed data" and misleading arguments to make a case against our CRE mechanism of the ozone hole and CFC-warming mechanism of global climate change. They make the groundless assertion that the CRE theory cannot be considered as an independent process for ozone loss in the polar stratosphere. Their claim that the impact of the CRE mechanism on polar chlorine activation and ozone loss in the stratosphere would be limited does not agree with the observed data over the past decades. They also make many contradictory and fact-distorting arguments that "There is no polar ozone loss in darkness, there is no apparent 11-year periodicity in polar total ozone measurements, the age of air in the polar lower stratosphere is much older than 1-2 years, and the reported detection of a pronounced recovery (by about 20-25%) in Antarctic total ozone measurements by the year 2010 is in error." These assertions ignore and contradict a great deal of robust observed data from both laboratory and field measurements reported in the literature including their own publications. Their new argument for the photodissociation of CFCs on PSCs also contradicts their previous extraordinary efforts including the use of fabricated "ACE-FTS satellite data" to argue for no physical/chemical loss of CFCs in the winter lower polar stratosphere. Finally, they do not provide any scientific evidence to support their criticism for the no physical basis of the CFC-warming theory and its conclusions. In summary, their misleading arguments and false "data" do not change the convincing conclusion reached by robust observations in my recent paper that both the CRE mechanism and the CFC-warming mechanism not only provide new fundamental understandings of the O3 hole and global climate change but have superior predictive capabilities, compared with the conventional models.

Attenuation of fluorocarbons released from foam insulation in landfills.

PubMed

Scheutz, Charlotte; Dote, Yutaka; Fredenslund, Anders M; Mosbaek, Hans; Kjeldsen, Peter

2007-11-15

Chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) have been used as blowing agents (BAs) for foam insulation in home appliances and building materials, which after the end of their useful life are disposed of in landfills. The objective of this project was to evaluate the potential for degradation of BAs in landfills, and to develop a landfill model, which could simulate the fate of BAs in landfills. The investigation was performed by use of anaerobic microcosm studies using different types of organic waste and anaerobic digested sludge as inoculum. The BAs studied were CFC-11, CFC-12, HCFC-141b, HFC-134a, and HFC-245fa. Experiments considering the fate of some of the expected degradations products of CFC-11 and CFC-12 were included like HCFC-21, HCFC-22, HCFC-31, HCFC-32, and HFC-41. Degradation of all studied CFCs and HCFCs was observed regardless the type of waste used. In general, the degradation followed first-order kinetics. CFC-11 was rapidly degraded from 590 microg L(-1) to less than 5 microg L(-1) within 15-20 days. The degradation pattern indicated a sequential production of HCFC-21, HCFC-31, and HFC-41. However, the production of degradation products did not correlate with a stoichiometric removal of CFC-11 indicating that other degradation products were produced. HCFC-21 and HCFC-31 were further degraded whereas no further degradation of HFC-41 was observed. The degradation rate coefficient was directly correlated with the number of chlorine atoms attached to the carbon. The highest degradation rate coefficient was obtained for CFC-11, whereas lower rates were seen for HCFC-21 and HCFC-31. Equivalent results were obtained for CFC-12. HCFC-141b was also degraded with rates comparable to HCFC-21 and CFC-12. Anaerobic degradation of the studied HFCs was not observed in any of the experiments within a run time of up to 200 days. The obtained degradation rate coefficients were used as input for an extended version of an existing landfill fate model incorporating a time dependent BA release from co-disposed foam insulation waste. Predictions with the model indicate that the emission of foam released BAs may be strongly attenuated by microbial degradation reactions. Sensitivity analysis suggests that there is a need for determination of degradation rates under more field realistic scenarios.

Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies

NASA Astrophysics Data System (ADS)

Hoffmann, L.; Hoppe, C. M.; Müller, R.; Dutton, G. S.; Gille, J. C.; Griessbach, S.; Jones, A.; Meyer, C. I.; Spang, R.; Volk, C. M.; Walker, K. A.

2014-06-01

Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their global loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer-tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 yr for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47±0.08 and a CFC-12 lifetime of 111(96-132) yr for ACE-FTS, a ratio of 0.46±0.07 and a lifetime of 112(97-133) yr for HIRDLS, and a ratio of 0.46±0.08 and a lifetime of 112(96-135) yr for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.47±0.04 and the CFC-12 lifetime estimate is 112(102-123) yr. These results agree with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43-67) yr and 102(88-122) yr, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled model we found a CFC-11/CFC-12 lifetime ratio of 0.48±0.07 and a CFC-12 lifetime of 110(95-129) yr, based on a ten-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers.

Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies

NASA Astrophysics Data System (ADS)

Hoffmann, L.; Hoppe, C. M.; Müller, R.; Dutton, G. S.; Gille, J. C.; Griessbach, S.; Jones, A.; Meyer, C. I.; Spang, R.; Volk, C. M.; Walker, K. A.

2014-11-01

Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their stratospheric loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer-tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 years for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47±0.08 and a CFC-12 lifetime of 112(96-133) years for ACE-FTS, a ratio of 0.46±0.07 and a lifetime of 113(97-134) years for HIRDLS, and a ratio of 0.46±0.08 and a lifetime of 114(98-136) years for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.46±0.04 and the CFC-12 lifetime estimate is 113(103-124) years. These results agree with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43-67) years and 102(88-122) years, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled model we found a CFC-11/CFC-12 lifetime ratio of 0.48±0.07 and a CFC-12 lifetime of 110(95-129) years, based on a 10-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers.

Measurements of HFC-134a and HCFC-22 in groundwater and unsaturated-zone air: implications for HFCs and HCFCs as dating tracers

USGS Publications Warehouse

Haase, Karl B.; Busenberg, Eurybiades; Plummer, Niel; Casile, Gerolamo; Sanford, Ward E.

2014-01-01

A new analytical method using gas chromatography with an atomic emission detector (GC–AED) was developed for measurement of ambient concentrations of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) in soil, air, and groundwater, with the goal of determining their utility as groundwater age tracers. The analytical detection limits of HCFC-22 (difluorochloromethane, CHClF2) and HFC-134a (1,2,2,2-tetrafluoroethane, C2H2F4) in 1 L groundwater samples are 4.3 × 10− 1 and 2.1 × 10− 1 pmol kg− 1, respectively, corresponding to equilibrium gas-phase mixing ratios of approximately 5–6 parts per trillion by volume (pptv). Under optimal conditions, post-1960 (HCFC-22) and post-1995 (HFC-134a) recharge could be identified using these tracers in stable, unmixed groundwater samples. Ambient concentrations of HCFC-22 and HFC-134a were measured in 50 groundwater samples from 27 locations in northern and western parts of Virginia, Tennessee, and North Carolina (USA), and 3 unsaturated-zone profiles were collected in northern Virginia. Mixing ratios of both HCFC-22 and HFC-134a decrease with depth in unsaturated-zone gas profiles with an accompanying increase in CO2 and loss of O2. Apparently, ambient concentrations of HCFC-22 and HFC-134a are readily consumed by methanotrophic bacteria under aerobic conditions in the unsaturated zone. The results of this study indicate that soils are a sink for these two greenhouse gases. These observations contradict the previously reported results from microcosm experiments that found that degradation was limited above-ambient HFC-134a. The groundwater HFC and HCFC concentrations were compared with concentrations of chlorofluorocarbons (CFCs, CFC-11, CFC-12, CFC-113) and sulfur hexafluoride (SF6). Nearly all samples had measured HCFC-22 or HFC-134a that were below concentrations predicted by the CFCs and SF6, with many samples showing a complete loss of HCFC-22 and HFC-134a. This study indicates that HCFC-22 and HFC-134a are not conservative as environmental tracers and leaves in question the usefulness of other HCFCs and HFCs as candidate age tracers.

HFC-152a and HFC-134a emission estimates and characterization of CFCs, CFC replacements, and other halogenated solvents measured during the 2008 ARCTAS campaign (CARB phase) over the South Coast Air Basin of California

NASA Astrophysics Data System (ADS)

Barletta, B.; Nissenson, P.; Meinardi, S.; Dabdub, D.; Sherwood Rowland, F.; Vancuren, R. A.; Pederson, J.; Diskin, G. S.; Blake, D. R.

2011-03-01

This work presents results from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Whole air samples were obtained on board research flights that flew over California during June 2008 and analyzed for selected volatile organic compounds, including several halogenated species. Samples collected over the South Coast Air Basin of California (SoCAB), which includes much of Los Angeles (LA) County, were compared with samples from inflow air masses over the Pacific Ocean. The levels of many halocarbon species were enhanced significantly over the SoCAB, including compounds regulated by the Montreal Protocol and subsequent amendments. Emissions estimates of HFC-152a (1,1-difluoroethane, CH3CHF2; 0.82 ± 0.11 Gg) and HFC-134a (1,1,1,2-tetrafluoroethane, CH2FCF3; 1.16 ± 0.22 Gg) in LA County for 2008 were obtained using the observed HFC:carbon monoxide (CO) enhancement ratio. Emission rates also were calculated for the SoCAB (1.60 ± 0.22 Gg yr-1 for HFC-152a and 2.12 ± 0.28 Gg yr-1 for HFC-134a) and then extrapolated to the United States (32 ± 4 Gg yr-1 for HFC-152a and 43 ± 6 Gg yr-1 for HFC-134a) using population data. In addition, emission rates of the two HFCs in LA County and SoCAB were calculated by a second method that utilizes air quality modeling. Emissions estimates obtained using both methods differ by less than 25% for the LA County and less than 45% for the SoCAB.

Abiotic Formation of Methyl Halides in the Terrestrial Environment

NASA Astrophysics Data System (ADS)

Keppler, F.

2011-12-01

Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will include a consideration on how stable isotope studies assisted advancements in this subject area. For example, it has been shown that the methoxyl groups of lignin and pectin which together constitute the bulk of the C1 plant pool have a carbon isotope signature significantly depleted in 13C. Plant-derived C1 volatile organic compounds (VOCs) are also highly depleted in 13C compared with Cn+1 VOCs. These observations suggest that the plant methoxyl pool is the predominant source of methyl halides released from senescent and dead plant litter. The distinct 13C depletion of plant methoxyl groups and naturally produced methyl halides may provide a helpful tool in constraining complex environmental processes and therefore improve our understanding of the global cycles of atmospheric methyl halides.

Relation of Chlorofluorocarbon Ground-Water Age Dates to Water Quality in Aquifers of West Virginia

USGS Publications Warehouse

,; Kurt, J.; Kozar, Mark D.

2007-01-01

The average apparent age of ground water in fractured-bedrock aquifers in West Virginia was determined using chlorofluorocarbon (CFC) dating methods. Since the introduction of CFC gases as refrigerants in the late 1930s, atmospheric concentrations have increased until production ceased in the mid-1990s. CFC dating methods are based on production records that date to the early 1940s, and the preservation of atmospheric CFC concentrations in ground water at the time of recharge. As part of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) and Ambient Ground-Water Monitoring Network (AGN) programs in West Virginia from 1997 to 2005, 80 samples from the Appalachian Plateaus Physiographic Province, 27 samples from the Valley and Ridge Physiographic Province, and 5 samples from the Ohio River alluvial aquifers were collected to estimate ground-water ages in aquifers of West Virginia. Apparent CFC ages of water samples from West Virginia aquifers ranged from 5.8 to 56 years. In the Appalachian Plateaus, topographically driven ground-water flow is evident from apparent ages of water samples from hilltop, hillside, and valley settings (median apparent ages of 12, 14, and 25 years, respectively). Topographic setting was the only factor that was found to be related to apparent ground-water age in the Plateaus at the scale of this study. Similar relations were not found in Valley and Ridge aquifers, indicating that other factors such as bedding or geologic structure may serve larger roles in controlling ground-water flow in that physiographic province. Degradation of CFCs was common in samples collected from methanogenic/anoxic aquifers in the Appalachian Plateaus and suboxic to anoxic aquifers in the Valley and Ridge. CFC contamination was most common in Ohio River alluvial aquifers and carbonate units of the Valley and Ridge, indicating that these highly transmissive surficial aquifers are the most vulnerable to water-quality degradation and may contain wastewater from domestic or industrial sources with CFC concentrations greater than modern atmospheric levels. However, based on a lack of detections of the volatile organic compounds analyzed for in most of the water samples collected for this and similar USGS investigations, ground-water resources of West Virginia used for public and private consumption do not appear to be routinely affected by anthropogenic activities despite their young apparent age.

Impact of Future Volcanic Eruptions on Stratospheric Ozone

NASA Astrophysics Data System (ADS)

Wilmouth, D. M.; Klobas, J. E.; Weisenstein, D.; Anderson, J. G.; Salawitch, R. J.

2017-12-01

Due to the anthropogenic release of chlorine-containing chemicals such as chlorofluorocarbons into the atmosphere in the twentieth century, a large volcanic eruption occurring today would initiate chemical reactions that reduce the thickness of the ozone layer. In the future, when atmospheric levels of chlorine are reduced, large volcanic eruptions are instead expected to increase the thickness of the ozone layer, but important details relevant to this shift in volcanic impact are not well known. Here we use the AER-2D chemical transport model to simulate a Pinatubo-like volcanic eruption in contemporary and future atmospheres. In particular, we explore the sensitivity of column ozone to volcanic eruption for four different climate change scenarios over the remainder of this century and also establish the importance of bromine-containing very short-lived substances (VSLS) in determining whether future eruptions will lead to ozone depletion. We find that the ozone layer will be vulnerable to volcanic perturbation for considerably longer than previously believed. Finally, we consider the impact on column ozone of inorganic halogens being co-injected into the stratosphere following future explosive eruptions using realistic hydrogen halide to sulfur dioxide ratios.

Radiative and Dynamical Feedbacks Limit the Climate Response to Extremely Large Volcanic Eruptions

NASA Astrophysics Data System (ADS)

Wade, D. C.; Vidal, C. M.; Keeble, J. M.; Griffiths, P. T.; Archibald, A. T.

2017-12-01

Explosive volcanic eruptions are a major cause of chemical and climatic perturbations to the atmosphere, injecting chemically and radiatively active species such as sulfur dioxide (SO2) into the stratosphere. The rate determining step for sulfate aerosol production is SO2 + OH +M → HSO3 +M. This means that chemical feedbacks on the hydroxyl radical, OH, can modulate the production rate of sulfate aerosol and hence the climate effects of large volcanic eruptions. Radiative feedbacks due to aerosols, ozone and sulfur dioxide and subsequent dynamical changes also affect the evolution of the aerosol cloud. Here we assess the role of radiative and chemical feedbacks on sulfate aerosol production using UM-UKCA, a chemistry-climate model coupled to GLOMAP, a prognostic modal aerosol model. A 200 Tg (10x Pinatubo) emission scenario is investigated. Accounting for radiative feedbacks, the SO2 lifetime is 55 days compared to 26 days in the baseline 20 Tg (1x Pinatubo) simulation. By contrast, if all radiative feedbacks are neglected the lifetime is 73 days. Including radiative feedbacks reduces the SO2 lifetime: heating of the lower stratosphere by aerosol increases upwelling and increases transport of water vapour across the tropopause, increasing OH concentrations. The maximum effective radius of the aerosol particles increases from 1.09 µm to 1.34 µm as the production of aerosol is quicker. Larger and fewer aerosol particles are produced which are less effective at scattering shortwave radiation and will more quickly sediment from the stratosphere. As a result, the resulting climate cooling by the eruption will be less strong when accounting for these radiative feedbacks. We illustrate the consequences of these effects for the 1257 Samalas eruption, the largest common era volcanic eruption, using UM-UKCA in a coupled atmosphere-ocean configuration. As a potentially halogen rich eruption, we investigate the differing ozone response to halogen-rich and halogen-poor eruption scenarios against a pre-industrial baseline climate. This has important implications for future volcanic eruptions as ClOx reduces in response to the cessation of chlorofluorocarbon emissions.

Comparison of halocarbon measurements in an atmospheric dry whole air sample.

PubMed

Rhoderick, George C; Hall, Bradley D; Harth, Christina M; Kim, Jin Seog; Lee, Jeongsoon; Montzka, Stephen A; Mühle, Jens; Reimann, Stefan; Vollmer, Martin K; Weiss, Ray F

The growing awareness of climate change/global warming, and continuing concerns regarding stratospheric ozone depletion, will require continued measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track atmospheric mole fractions and assess the impact of policy on emission rates, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. Precise measurements of these species aid in determining small changes in their atmospheric abundance. A common source of standards/scales and/or well-documented agreement of different scales used to calibrate the measurement instrumentation are key to understanding many sets of data reported by researchers. This report describes the results of a comparison study among National Metrology Institutes and atmospheric research laboratories for the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11), and 1,1,2-trichlorotrifluoroethane (CFC-113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC-22) and 1-chloro-1,1-difluoroethane (HCFC-142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC-134a), all in a dried whole air sample. The objective of this study is to compare calibration standards/scales and the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. The results of this study show agreement among four independent calibration scales to better than 2.5% in almost all cases, with many of the reported agreements being better than 1.0%.

Application of environmental tracers to mixing, evolution, and nitrate contamination of ground water in Jeju Island, Korea

USGS Publications Warehouse

Koh, D.-C.; Plummer, Niel; Kip, Solomon D.; Busenberg, E.; Kim, Y.-J.; Chang, H.-W.

2006-01-01

Tritium/helium-3 (3H/3He) and chlorofluorocarbons (CFCs) were investigated as environmental tracers in ground water from Jeju Island (Republic of Korea), a basaltic volcanic island. Ground-water mixing was evaluated by comparing 3H and CFC-12 concentrations with lumped-parameter dispersion models, which distinguished old water recharged before the 1950s with negligible 3H and CFC-12 from younger water. Low 3H levels in a considerable number of samples cannot be explained by the mixing models, and were interpreted as binary mixing of old and younger water; a process also identified in alkalinity and pH of ground water. The ground-water CFC-12 age is much older in water from wells completed in confined zones of the hydro-volcanic Seogwipo Formation in coastal areas than in water from the basaltic aquifer. Major cation concentrations are much higher in young water with high nitrate than those in uncontaminated old water. Chemical evolution of ground water resulting from silicate weathering in basaltic rocks reaches the zeolite-smectite phase boundary. The calcite saturation state of ground water increases with the CFC-12 apparent (piston flow) age. In agricultural areas, the temporal trend of nitrate concentration in ground water is consistent with the known history of chemical fertilizer use on the island, but increase of nitrate concentration in ground water is more abrupt after the late 1970s compared with the exponential growth of nitrogen inputs. ?? 2005 Elsevier B.V. All rights reserved.

Solid-cryogen-stabilized, cable-in-conduit (CIC) superconducting cables

NASA Astrophysics Data System (ADS)

Voccio, J. P.; Michael, P. C.; Bromberg, L.; Hahn, S.

2015-12-01

This paper considers the use of a solid cryogen as a means to stabilize, both mechanically and thermally, magnesium diboride (MgB2) superconducting strands within a dual-channel cable-in-conduit (CIC) cable for use in AC applications, such as a generator stator winding. The cable consists of two separate channels; the outer channel contains the superconducting strands and is filled with a fluid (liquid or gas) that becomes solid at the device operating temperature. Several options for fluid will be presented, such as liquid nitrogen, hydrocarbons and other chlorofluorocarbons (CFCs) that have a range of melting temperatures and volumetric expansions (from solid at operating temperature to fixed volume at room temperature). Implications for quench protection and conductor stability, enhanced through direct contact with the solid cryogen, which has high heat capacity and thermal conductivity (compared with helium gas), will be presented. Depending on the cryogen, the conductor will be filled initially either with liquid at atmospheric conditions or a gas at high pressure (∼100 atm). After cooldown, the cryogen in the stranded-channel will be solid, essentially locking the strands in place, preventing strand motion and degradation due to mechanical deformation while providing enhanced thermal capacity for stability and protection. The effect of cryogen porosity is also considered. The relatively high heat capacity of solid cryogens at these lower temperatures (compared to gaseous helium) enhances the thermal stability of the winding. During operation, coolant flow through the open inner channel will minimize pressure drop.

Comparison of halocarbon measurements in an atmospheric dry whole air sample

PubMed Central

Hall, Bradley D.; Harth, Christina M.; Kim, Jin Seog; Lee, Jeongsoon; Montzka, Stephen A.; Mühle, Jens; Reimann, Stefan; Vollmer, Martin K.; Weiss, Ray F.

2015-01-01

The growing awareness of climate change/global warming, and continuing concerns regarding stratospheric ozone depletion, will require continued measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track atmospheric mole fractions and assess the impact of policy on emission rates, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. Precise measurements of these species aid in determining small changes in their atmospheric abundance. A common source of standards/scales and/or well-documented agreement of different scales used to calibrate the measurement instrumentation are key to understanding many sets of data reported by researchers. This report describes the results of a comparison study among National Metrology Institutes and atmospheric research laboratories for the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11), and 1,1,2-trichlorotrifluoroethane (CFC-113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC-22) and 1-chloro-1,1-difluoroethane (HCFC-142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC-134a), all in a dried whole air sample. The objective of this study is to compare calibration standards/scales and the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. The results of this study show agreement among four independent calibration scales to better than 2.5% in almost all cases, with many of the reported agreements being better than 1.0%. PMID:26753167

Sputtering yields of carbon based materials under high particle flux with low energy

NASA Astrophysics Data System (ADS)

Nakamura, K.; Nagase, A.; Dairaku, M.; Akiba, M.; Araki, M.; Okumura, Y.

1995-04-01

A new ion source which can produce high particle flux beams at low energies has been developed. This paper presents preliminary results on the sputtering yield of the carbon fiber reinforced composites (CFCs) measured with the new ion source. The sputtering yields of 1D and 2D CFCs, which are candidate materials for the divertor armour tiles, have been measured by the weight loss method under the hydrogen and deuterium particle fluxes of 2 ˜ 7 × 10 20/m 2 s at 50 ˜ 150 eV. Preferential sputtering of the matrix was observed on CFCs which included the matrix of 40 ˜ 60 w%. The energy dependence of the sputtering yields was weak. The sputtering yields of CFCs normally irradiated with deuterium beam were from 0.073 to 0.095, and were around three times larger than those with hydrogen beam.

Alignment of classification paradigms for communication abilities in children with cerebral palsy

PubMed Central

Hustad, Katherine C.; Oakes, Ashley; McFadd, Emily; Allison, Kristen M.

2015-01-01

Aim We examined three communication ability classification paradigms for children with cerebral palsy (CP): the Communication Function Classification System (CFCS), the Viking Speech Scale (VSS), and the Speech Language Profile Groups (SLPG). Questions addressed inter-judge reliability, whether the VSS and the CFCS captured impairments in speech and language, and whether there were differences in speech intelligibility among levels within each classification paradigm. Method 80 children (42 males) with a range of types and severity levels of CP participated (mean age, 60 months; SD 4.8 months). Two speech-language pathologists classified each child via parent-child interaction samples and previous experience with the children for the CFCS and VSS, and uisng quantitative speech and language assessment data for the SLPG. Intelligibility scores were obtained using standard clinical intelligibility measurement. Results Kappa values were .67 (95% CI [.55, .79]) for the CFCS, .82 (95% CI [.72, .92]), for the VSS, .95 (95% CI [.72, .92]) for the SLPG. Descriptively, reliability within levels of each paradigm varied, with the lowest agreement occurring within the CFCS at levels II (42%), III (40%), and IV (61%). Neither the CFCS nor the VSS were sensitive to language impairments captured by the SLPG. Significant differences in speech intelligibility were found among levels for all classification paradigms. Interpretation Multiple tools are necessary to understand speech, language, and communication profiles in children with CP. Characterization of abilities at all levels of the ICF will advance our understanding of the ways that speech, language, and communication abilities present in children with CP. PMID:26521844

Atmospheric Science and the CFC Industry

NASA Astrophysics Data System (ADS)

Steed, J. M.

2012-12-01

Industry involvement with developing atmospheric science and subsequent regulations to protect ozone was unusual. Chlorofluorocarbon manufacturers were research-based businesses accustomed to understanding the science behind product-related issues. When Lovelock's measurements in 1971 implied most of the cumulative production of CFCs remained in the atmosphere, global CFC producers funded academic research to identify natural sinks for the materials. The Fluorocarbon Program Panel (FPP) began in 1972, but changed focus to atmospheric photochemistry following Rowland and Molina's work in 1974. Despite early vociferous opposition, especially by the CFC-using aerosol industry, to any regulations, leaders among the producers worked to build their scientific understanding, expanding FPP funding and launching internal work in modeling and ozone trend analysis. The key first question for industry was not how much depletion might occur, but whether it would occur at all. If so, regardless of the amount, regulations and a major transition would be required in CFC-using industries, and the response would need to be global and prompt. So long as that basic question was in doubt, some businesses and countries would resist the economic cost of action. In the meantime, the producing industry worked to identify potential alternatives and to communicate atmospheric science to the downstream industries. Although the industry science effort was often disparaged as an attack on "real" science, my only assignment when I joined DuPont's Central Research Department in 1979 was to understand and contribute to the science, keeping both the company and our customers informed. Our modeling results were published freely. FPP funding led to better knowledge of the ClO + O rate constant, significantly increasing depletion in model calculations; supported the development of the techniques used to measure in situ atmospheric ClO, so important in later strengthening the case for chlorine-catalyzed depletion; and supported international participation in several global collaborations led by NASA. By the mid-1980s, the combination of renewed growth in global production and modelers' unanimity that depletion eventually would occur in any scenario of sustained growth led most of the industry to support actively the UN-led international negotiations. Knowing that any limit to global growth would eventually stimulate development of replacements, broad agreement was far more important than any specific target for limiting growth. The Montreal Protocol achieved that agreement, and support from the broad US industry coalition in the Alliance for Responsible CFC Policy was instrumental in its approval by the Reagan administration. Just as Rowland's work in 1974 had driven the industry to understand and contribute to atmospheric science, his participation in the ozone trends panel results announced in March, 1988 led to another shift. The combination of solid links between CFCs and stratospheric chlorine, between chlorine and ozone depletion, at least at the poles, and the likely presence of depletion at mid-latitudes, whether or not caused by chlorine, led DuPont to announce a week later a complete phaseout of CFCs. Broader industry support followed, culminating what is still the best example of government, industry, scientific, and environmentalist collaboration on a global scale.

Erosion of newly developed CFCs and Be under disruption heat loads

NASA Astrophysics Data System (ADS)

Nakamura, K.; Akiba, M.; Araki, M.; Dairaku, M.; Sato, K.; Suzuki, S.; Yokoyama, K.; Linke, J.; Duwe, R.; Bolt, H.; Roedig, M.

1996-10-01

An evaluation of the erosion under disruption heat loads is very important to the lifetime prediction of divertor armour tiles of next fusion devices such as ITER. In particular, erosion data on CFCs (carbon fiber reinforced composites) and beryllium (Be) as the armour materials is urgently required in the ITER design. For CFCs, high heat flux experiments on the newly developed CFCs with high thermal conductivity have been performed under the heat flux of around 800-2000 MW/m 2 and the pulse length of 2-5 ms in JAERI electron beam irradiation systems (JEBIS). As a result, the weight losses of B 4C doped CFCs after heating were almost same to those of the non doped CFC up to 5 wt% boron content. For Be, we have carried out our first disruption experiments on S65/C grade Be specimens in the Juelich divertor test facility in hot cells (JUDITH) facility as a frame work of the J—EU collaboration. The heating conditions were heat loads of 1250-5000 MW/m 2 for 2-8 ms, and the heated area was 3 × 3 mm 2. As a result, the protuberances of the heated area of Be were observed under the lower heat flux.

Identifying the Molecular Origin of Global Warming

NASA Technical Reports Server (NTRS)

Bera, Partha P.; Francisco, Joseph S.; Lee, Timothy J.

2009-01-01

We have investigated the physical characteristics of greenhouse gases (GHGs) to assess which properties are most important in determining the efficiency of a GHG. Chlorofluorcarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), nitrogen fluorides, and various other known atmospheric trace molecules have been included in this study. Compounds containing the halogens F or Cl have in common very polar X-F or X-Cl bonds, particularly the X-F bonds. It is shown that as more F atoms bond to the same central atom, the bond dipoles become larger as a result of the central atom becoming more positive. This leads to a linear increase in the total or integrated XF bond dipole derivatives for the molecule, which leads to a non-linear (quadratic) increase in infrared (IR) intensity. Moreover, virtually all of the X-F bond stretches occur in the atmospheric IR window as opposed to X-H stretches, which do not occur in the atmospheric window. It is concluded that molecules possessing several F atoms will always have a large radiative forcing parameter in the calculation of their global warming potential. Some of the implications for global warming and climate change are discussed.

Alignment of classification paradigms for communication abilities in children with cerebral palsy.

PubMed

Hustad, Katherine C; Oakes, Ashley; McFadd, Emily; Allison, Kristen M

2016-06-01

We examined three communication ability classification paradigms for children with cerebral palsy (CP): the Communication Function Classification System (CFCS), the Viking Speech Scale (VSS), and the Speech Language Profile Groups (SLPG). Questions addressed interjudge reliability, whether the VSS and the CFCS captured impairments in speech and language, and whether there were differences in speech intelligibility among levels within each classification paradigm. Eighty children (42 males, 38 females) with a range of types and severity levels of CP participated (mean age 60mo, range 50-72mo [SD 5mo]). Two speech-language pathologists classified each child via parent-child interaction samples and previous experience with the children for the CFCS and VSS, and using quantitative speech and language assessment data for the SLPG. Intelligibility scores were obtained using standard clinical intelligibility measurement. Kappa values were 0.67 (95% confidence interval [CI] 0.55-0.79) for the CFCS, 0.82 (95% CI 0.72-0.92) for the VSS, and 0.95 (95% CI 0.72-0.92) for the SLPG. Descriptively, reliability within levels of each paradigm varied, with the lowest agreement occurring within the CFCS at levels II (42%), III (40%), and IV (61%). Neither the CFCS nor the VSS were sensitive to language impairments captured by the SLPG. Significant differences in speech intelligibility were found among levels for all classification paradigms. Multiple tools are necessary to understand speech, language, and communication profiles in children with CP. Characterization of abilities at all levels of the International Classification of Functioning, Disability and Health will advance our understanding of the ways that speech, language, and communication abilities present in children with CP. © 2015 Mac Keith Press.

Evaluation for Practical Application of HFC Refrigerants

NASA Astrophysics Data System (ADS)

Uemura, Shigehiro; Noguchi, Masahiro; Inagaki, Sadayasu; Teraoka, Takuya

Production restriction of CFCs which are used for refrigerators and air conditioners has been implemented through the international mutual agreement approved by the Montreal Protocol. Due to the less impact on the ozone layer dep1etion, alternative refrigerants for CFCs had included HCFC-123 and HCFC-22. However, H CFC-123 and HCFC-22 do not completely prevent the ozone layer depletion. This paper presents the investigation results of HFC-125, H FC-143a, HFC-152a, and HFC-32 which prevent the ozone layer depletion and are candidates for alternatives of CFCs and HCFCs. The test results of thermal stability of these refrigerants are similar to those of CFC-12 and HCFC-22. The test results show that each refrigerant has different material compatibility. The test results of lubricant solubility show that synthetic oi1s are soluble in these refrigerants, but the mineral oils currently in use for CFCs and HCFCs are not. The refrigeration performance based on the calculated thermodynamic properties corresponds with that of the experimental results.

A historical look at chlorofluorocarbon refrigerants

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

Bhatti, M.S.

1999-07-01

A class of chemical compounds called chlorofluorocarbon refrigerants has been in widespread use since the 1930s in such diverse applications as refrigerants for refrigerating and air-conditioning systems, blowing agents for plastic foams, solvents for microelectronic circuitry and dry cleaning, sterilants for medical instruments, aerosol propellants for personal hygiene products and pesticides, and freezants for food. This paper describes the historical development of the chlorofluorocarbon refrigerants and gives brief biographical sketches of the inventors. 85 refs., 8 figs., 4 tabs.

Estimates of tracer-based piston-flow ages of groundwater from selected sites: National Water-Quality Assessment Program, 2006-2010

USGS Publications Warehouse

Shapiro, Stephanie D.; Plummer, Niel; Busenberg, Eurybiades; Widman, Peggy K.; Casile, Gerolamo C.; Wayland, Julian E.; Runkle, Donna L.

2012-01-01

Piston-flow age dates were interpreted from measured concentrations of environmental tracers from 812 National Water-Quality Assessment (NAWQA) Program groundwater sites from 27 Study Units across the United States. The tracers of interest include chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), and tritium/helium-3 (3H/3He). Tracer data compiled for this analysis were collected from 2006 to 2010 from groundwater wells in NAWQA studies, including: * Land-Use Studies (LUS, shallow wells, usually monitoring wells, located in recharge areas under dominant land-use settings), * Major-Aquifer Studies (MAS, wells, usually domestic supply wells, located in principal aquifers and representing the shallow drinking water supply), * Flow System Studies (FSS, networks of clustered wells located along a flowpath extending from a recharge zone to a discharge zone, preferably a shallow stream) associated with Land-Use Studies, and * Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) also associated with Land-Use Studies. Tracer data were evaluated using documented methods and are presented as aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF6), and tracer-based piston-flow ages. Selected ancillary data, such as redox data, well-construction data, and major dissolved-gas (N2, O2, Ar, CH4, and CO2) data, also are presented. Recharge temperature was inferred using climate data (approximated by mean annual air temperature plus 1°C [MAAT +1°C]) as well as major dissolved-gas data (N2-Ar-based) where available. The N2-Ar-based temperatures showed significantly more variation than the climate-based data, as well as the effects of denitrification and degassing resulting from reducing conditions. The N2-Ar-based temperatures were colder than the climate-based temperatures in networks where recharge was limited to the winter months when evapotranspiration was reduced. The tracer-based piston-flow ages compiled in this report are provided as a consistent means of reporting the tracer data. The tracer-based piston-flow ages may provide an initial interpretation of age in cases in which mixing is minimal and may aid in developing a basic conceptualization of groundwater age in an aquifer. These interpretations are based on the assumption that tracer transport is by advection only and that no mixing occurs. In addition, it is assumed that other uncertainties are minimized, including tracer degradation, sorption, contamination, or fractionation, and that terrigenic (natural) sources of tracers, and spatially variable atmospheric tracer concentrations are constrained.

2016 AMS Mario J. Molina Symposium

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

Zhang, Renyi

A named symposium to honor Dr. Mario J. Molina was held 10–14 January 2016, as part of the 96th American Meteorological Society (AMS) Annual Meeting in New Orleans, Louisiana. Dr. Molina first demonstrated that industrially produced chlorofluorocarbons (CFCs) decompose in the stratosphere and release chlorine atoms, leading to catalytic ozone destruction. His research in stratospheric chemistry was instrumental to the establishment of the 1987 United Nations Montreal Protocol to ban ozone-depleting substances worldwide. Dr. Molina’s contributions to preserving the planet Earth not only save the atmospheric ozone layer, but also protect the climate by reducing the emissions of greenhouse gases.more » He was awarded the 1995 Nobel Prize in Chemistry for his pioneering research in understanding the stratospheric ozone loss mechanism. In 2013, President Barack Obama announced Dr. Molina as a recipient of the Presidential Medal of Freedom. The 2016 AMS Molina Symposium honored Dr. Molina’s distinguished contributions to research related to atmospheric chemistry. The symposium contained an integrated theme related to atmospheric chemistry, climate, and policy. Dr. Molina delivered a keynote speech at the Symposium. The conference included invited keynote speeches and invited and contributed oral and poster sessions, and a banquet was held on Tuesday January 12, 2016. The symposium covered all aspects of atmospheric chemistry, with topics including (1) Stratospheric chemistry, (2) Tropospheric chemistry, (3) Aerosol nucleation, growth, and transformation, (4) Aerosol properties, (5) Megacity air pollution, and (6) Atmospheric chemistry laboratory, field, and modeling studies. This DOE project supported 14 scientists, including graduate students, post docs, junior research scientists, and non-tenured assistant professors to attend this symposium.« less

Environmental risk assessment of hydrofluoroethers (HFEs).

PubMed

Tsai, Wen-Tien

2005-03-17

Hydrofluoroethers (HFEs) are being used as third generation replacements to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and perfluorocarbons (PFCs) because of their nearly zero stratospheric ozone depletion and relatively low global warming potential. HFEs have been developed under commercial uses as cleaning solvents (incl., HFE-7500, C7F15OC2H5; HFE-7200, C4F9OC2H5; HFE-7100, C4F9CH3; HFE-7000, n-C3F7OCH3), blowing agents (incl., HFE-245mc, CF3CF2OCH3; HFC-356mec, CF3CHFCF2OCH3), refrigerants (incl., HFE-143a, CF3OCH3; HFE-134, CHF2OCHF2; HFE-245mc, CF3CF2OCH3), and dry etching agents in semiconductor manufacturing, (incl., HFE-227me, CF3OCHFCF3). From the environmental, ecological, and health points of view, it is important to understand their environmental risks for these HFEs from a diversity of commercial applications and industrial processes. This paper aims to introduce these HFEs with respect to physiochemical properties, commercial uses, and environmental hazards (i.e. global warming, photochemical potential, fire and explosion hazard, and environmental partition). Further, it addresses the updated data on the human toxicity, occupational exposure and potential health risk of commercial HFEs. It is concluded that there are few HFEs that still possess some environmental hazards, including global warming, flammability hazard and adverse effect of exposure. The partition coefficient for these HFEs has been estimated using the group contribution method; the values of logKow for commercial HFEs have been estimated to be below 3.5.

Calculated trends and the atmospheric abundance of 1,1,1,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, and 1-chloro-1,1-difluoroethane using automated in-situ gas chromatography-mass spectrometry measurements recorded at Mace Head, Ireland, from October 1994 to March 1997

NASA Astrophysics Data System (ADS)

Simmonds, P. G.; O'Doherty, S.; Huang, J.; Prinn, R.; Derwent, R. G.; Ryall, D.; Nickless, G.; Cunnold, D.

1998-01-01

The first in-situ measurements by automated gas chromatograph-mass spectrometer are reported for 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-dichloro-1-fluoroethane, (HCFC-141b), and 1-chloro-1,1-difluoroethane, (HCFC-142b). These compounds are steadily replacing the chlorofluorocarbons (CFCs) as refrigerants, foam-blowing agents, and solvents. The concentrations of all three compounds are shown to be rapidly increasing in the atmosphere, with 134a increasing at a rate of 2.05±0.02 ppt yr-1 over the 30 months of observations. Similarly, 141b and 142b increased at rates of 2.49±0.03 and 1.24±0.02 ppt yr-1, respectively, over the same period. The concentrations recorded at the atmospheric research station at Mace Head, Ireland, on January 1, 1996, the midpoint of the time series, were 3.67 ppt (134a), 7.38 ppt (141b), and 8.78 ppt (142b). From these observations we optimally estimate the HCFC and HFC emissions using a 12-box global model and OH concentrations derived from global 1,1,1-trichloroethane (CCl3CH3) measurements. Comparing two methods of estimating emissions with independent industry estimates shows satisfactory agreement for 134a and 141b, while for 142b, industry estimates are less than half those required to explain our observations.

Quality of Nevada's aquifers and their susceptibility to contamination, 1990-2004

USGS Publications Warehouse

Lopes, Thomas J.

2006-01-01

EXECUTIVE SUMMARY: In 1999, the U.S. Environmental Protection Agency introduced a rule to protect the quality of ground water in areas other than source-water protection areas. These other sensitive ground-water areas (OSGWA) are areas that are not currently but could eventually be used as a source of drinking water. To help determine whether a well is in an OSGWA, the Nevada Division of Environmental Protection needs statewide information on the susceptibility and vulnerability of Nevada's aquifer systems to contamination. This report presents an evaluation of the quality of ground water and susceptibility of Nevada's aquifer systems to anthropogenic contamination. Chemical tracers and statistical methods were used to assess the susceptibility of aquifer systems in Nevada. Chemical tracers included nitrate, pesticides, volatile organic compounds (VOCs), chlorofluorocarbons (CFCs), dissolved gases, and isotopes of hydrogen and oxygen. Ground-water samples were collected from 133 wells during August 2002 through October 2003. Logistic regression was done to estimate the probability of detecting nitrate above concentrations typically found in undeveloped areas. Nitrate is one of the most common anthropogenic contaminants that degrades ground-water quality, is commonly measured and is persistent, except in reducing conditions. These characteristics make nitrate a good indicator of aquifer susceptibility. Water-quality data for 5,528 wells were compiled into a database. The area around each well was characterized using information on explanatory variables that could be related to nitrate concentrations. Data also were used to characterize the quality of ground water in Nevada, including dissolved solids, nitrate, pesticide, and VOC concentrations.

Primitive erythropoiesis is regulated by miR-126 via nonhematopoietic Vcam-1+ cells.

PubMed

Sturgeon, Christopher M; Chicha, Laurie; Ditadi, Andrea; Zhou, Qinbo; McGrath, Kathleen E; Palis, James; Hammond, Scott M; Wang, Shusheng; Olson, Eric N; Keller, Gordon

2012-07-17

Primitive erythropoiesis defines the onset of hematopoiesis in the yolk sac of the early embryo and is initiated by the emergence of progenitors assayed as colony-forming cells (EryP-CFCs). EryP-CFCs are detected for only a narrow window during embryonic development, suggesting that both their initiation and termination are tightly controlled. Using the embryonic stem differentiation system to model primitive erythropoiesis, we found that miR-126 regulates the termination of EryP-CFC development. Analyses of miR-126 null embryos revealed that this miR also regulates EryP-CFCs in vivo. We identified vascular cell adhesion molecule-1 (Vcam-1) expressed by a mesenchymal cell population as a relevant target of miR-126. Interaction of EryP-CFCs with Vcam-1 accelerated their maturation to ßh1-globin(+) and Ter119(+) cells through a Src family kinase. These findings uncover a cell nonautonomous regulatory pathway for primitive erythropoiesis that may provide insight into the mechanism(s) controlling the developmental switch from primitive to definitive hematopoiesis. Copyright © 2012 Elsevier Inc. All rights reserved.

Pharmacokinetic-based prediction of real-life dosing of extended half-life clotting factor concentrates on hemophilia

PubMed Central

Gherardini, Stefano

2018-01-01

The improvement of clotting factor concentrates (CFCs) has undergone an impressive boost during the last six years. Since 2010, several new recombinant factor (rF)VIII/IX concentrates entered phase I/II/III clinical trials. The improvements are related to the culture of human embryonic kidney (HEK) cells, post-translational glycosylation, PEGylation, and co-expression of the fragment crystallizable (Fc) region of immunoglobulin (Ig)G1 or albumin genes in the manufacturing procedures. The extended half-life (EHL) CFCs allow an increase of the interval between bolus administrations during prophylaxis, a very important advantage for patients with difficulties in venous access. Although the inhibitor risk has not been fully established, phase III studies have provided standard prophylaxis protocols, which, compared with on-demand treatment, have achieved very low annualized bleeding rates (ABRs). The key pharmacokinetics (PK) parameter to tailor patient therapy is clearance, which is more reliable than the half-life of CFCs; the clearance considers the decay rate of the drug concentration–time profile, while the half-life considers only the half concentration of the drug at a given time. To tailor the prophylaxis of hemophilia patients in real-life, we propose two formulae (expressed in terms of the clearance, trough and dose interval between prophylaxis), respectively based on the one- and two-compartmental models (CMs), for the prediction of the optimal single dose of EHL CFCs. Once the data from the time decay of the CFCs are fitted by the one- or two-CMs after an individual PK analysis, such formulae provide to the treater the optimal trade-off among trough and time-intervals between boluses. In this way, a sufficiently long time-interval between bolus administration could be guaranteed for a wider class of patients, with a preassigned level of the trough. Finally, a PK approach using repeated dosing is discussed, and some examples with new EHL CFCs are shown. PMID:29899890

Pharmacokinetic and pharmacodynamic comparison of hydrofluoroalkane and chlorofluorocarbon formulations of budesonide

PubMed Central

Clearie, Karine L; Williamson, Peter A; Meldrum, Karen; Gillen, Michael; Carlsson, Lars-Goran; Carlholm, Marie; Ekelund, Jan; Lipworth, Brian J

2011-01-01

AIMS A hydrofluoroalkane formulation of budesonide pressurized metered-dose inhaler has been developed to replace the existing chlorofluorocarbon one. The aim of this study was to evaluate the pharmacokinetic and pharmacodynamic characteristics of both formulations. METHODS Systemic bioavailability and bioactivity of both hydrofluoroalkane and chlorofluorocarbon pressurized metered-dose inhaler formulations at 800 µg twice daily was determined during a randomized crossover systemic pharmacokinetic/pharmacodynamic study at steady state in healthy volunteers. Measurements included the following: plasma cortisol AUC24h[area under the concentration-time curve (0–24 h)], budesonide AUC0–12h and Cmax. Clinical efficacy was determined during a randomized crossover pharmacodynamic study in asthmatic patients receiving 200 µg followed by 800 µg budesonide via chlorofluorocarbon or hydrofluoroalkane pressurized metered-dose inhaler each for 4 weeks. Methacholine PC20 (primary outcome), exhaled nitric oxide, spirometry, peak expiratory flow and symptoms were evaluated. RESULTS In the pharmacokinetic study, there were no differences in cortisol, AUC0–12h[area under the concentration-time curve (0–12 h)], Tmax (time to maximum concentration) or Cmax (peak serum concentration) between the hydrofluoroalkane and chlorofluorocarbon pressurized metered-dose inhaler. The ratio of budesonide hydrofluoroalkane vs. chlorofluorocarbon pressurized metered-dose inhaler for cortisol AUC24h was 1.02 (95% confidence interval 0.93–1.11) and budesonide AUC0–12h was 1.03 (90% confidence interval 0.9–1.18). In the asthma pharmacodynamic study, there was a significant dose response (P < 0.0001) for methacholine PC20 (provocative concentration of methacholine needed to produce a 20% fall in FEV1) with a relative potency ratio of 1.10 (95% confidence interval 0.49–2.66), and no difference at either dose. No significant differences between formulations were seen with the secondary outcome variables. CONCLUSIONS Hydrofluoroalkane and chlorofluorocarbon formulations of budesonide were therapeutically equivalent in terms of relative lung bioavailability, airway efficacy and systemic effects. PMID:21395643

Postmarketing surveillance study of a non-chlorofluorocarbon inhaler according to the safety assessment of marketed medicines guidelines

PubMed Central

Ayres, J G; Frost, C D; Holmes, W F; Williams, D R R; Ward, S M

1998-01-01

Objective To evaluate the safety of a non-chlorofluorocarbon metered dose salbutamol inhaler. Design This was a postmarketing surveillance study, conducted under formal guidelines for company sponsored safety assessment of marketed medicines (SAMM). A non-randomised, non-interventional, observational design compared patients prescribed metered doses of salbutamol delivered by inhalers using either hydrofluoroalkane or chlorofluorocarbon as the propellant. Follow up was three months. Setting 646 general practices throughout the United Kingdom. Subjects 6614 patients with obstructive airways disease (1667 patient years of exposure). Main outcome measures Proportions of patients who were: admitted to hospital for respiratory diseases, reported adverse side effects, or withdrew because of adverse affects. Results There were no significant differences between the hydrofluoroalkane (HFA 134a) and chlorofluorocarbon inhaler groups in relation to the proportions of patients admitted to hospital for respiratory diseases (odds ratio 0.75; 95% confidence interval 0.51 to 1.08) or the proportions who reported adverse events (1.01; 0.88 to 1.17). However, more patients using the hydrofluoroalkane inhaler than the chlorofluorocarbon inhaler withdrew because of adverse events (3.8% and 0.9% respectively). Conclusion The hydrofluoroalkane inhaler was as safe as the chlorofluorocarbon inhaler when judged by hospital admissions and adverse affects. The study design successfully fulfilled the recommendations of the guidelines. Differences between postmarketing surveillance studies and randomised clinical trials in assessing safety were identified. These may lead to difficulties in the design of postmarketing surveillance studies. Key messagesCredibility of postmarketing surveillance studies is expected to increase after the introduction of guidelines covering their conduct The study design successfully fulfilled the requirements of these guidelines in terms of the number, rate, and geographical spread of patients recruitedSafety of salbutamol inhalers using hydrofluoroalkane and chlorofluorocarbon as propellants is similarImportant differences in study design/conduct and outcome between a postmarketing surveillance study and a randomised clinical trial merit further consideration. PMID:9756813

Preparing for climate change.

PubMed

Holdgate, M

1989-01-01

There is a distinct probability that humankind is changing the climate and at the same time raising the sea level of the world. The most plausible projections we have now suggest a rise in mean world temperature of between 1 degree Celsius and 2 degrees Celsius by 2030--just 40 years hence. This is a bigger change in a smaller period than we know of in the experience of the earth's ecosystems and human societies. It implies that by 2030 the earth will be warmer than at any time in the past 120,000 years. In the same period, we are likely to see a rise of 15-30 centimeters in sea level, partly due to the melting of mountain glaciers and partly to the expansion of the warmer seas. This may not seem much--but it comes on top of the 12-centimeter rise in the past century and we should recall that over 1/2 the world's population lives in zones on or near coasts. A quarter meter rise in sea level could have drastic consequences for countries like the Maldives or the Netherlands, where much of the land lies below the 2-meter contour. The cause of climate change is known as the 'greenhouse effect'. Greenhouse glass has the property that it is transparent to radiation coming in from the sun, but holds back radiation to space from the warmed surfaces inside the greenhouse. Certain gases affect the atmosphere in the same way. There are 5 'greenhouse gases' and we have been roofing ourselves with them all: carbon dioxide concentrations in the atmosphere have increased 25% above preindustrial levels and are likely to double within a century, due to tropical forest clearance and especially to the burning of increasing quantities of coal and other fossil fuels; methane concentrations are now twice their preindustrial levels as a result of releases from agriculture; nitrous oxide has increased due to land clearance for agriculture, use of fertilizers, and fossil fuel combustion; ozone levels near the earth's surface have increased due mainly to pollution from motor vehicles; and chlorofluorocarbons (CFCs) have been released in great quantities through their use in aerosol sprays, refrigerator fluids, and insulating foams. We can get rid of CFCs and curb the pollutants generating ozone, but it will be difficult to put the brake on either methane or nitrous oxide. And the reduction in carbon dioxide emissions will demand major changes in energy policy as well as action to slow deforestation. It appears that we are already committed to rising temperatures and sea levels. The question is by how much, in which areas? A number of things can be done to prepare for these changes: Governments must recognize that there is a problem; Better models must be worked out, especially to define where the greatest impacts from climate change and sea level rise will hit; Reference scenarios must be developed to see what the impacts are likely to be in ecological, agricultural, social and economic terms; Every country should develop "avoidance strategies" to minimize risk (for example, by not building on land likely to be flooded); We must cut down on the amount of greenhouse gases released into the atmosphere from human activities, by eliminating CFCs and adopting energy conservation programs and other measures to minimize CO2 release; Global agreements to protect the atmosphere are needed. full text

Inter-Relationships of Functional Status in Cerebral Palsy: Analyzing Gross Motor Function, Manual Ability, and Communication Function Classification Systems in Children

ERIC Educational Resources Information Center

Hidecker, Mary Jo Cooley; Ho, Nhan Thi; Dodge, Nancy; Hurvitz, Edward A.; Slaughter, Jaime; Workinger, Marilyn Seif; Kent, Ray D.; Rosenbaum, Peter; Lenski, Madeleine; Messaros, Bridget M.; Vanderbeek, Suzette B.; Deroos, Steven; Paneth, Nigel

2012-01-01

Aim: To investigate the relationships among the Gross Motor Function Classification System (GMFCS), Manual Ability Classification System (MACS), and Communication Function Classification System (CFCS) in children with cerebral palsy (CP). Method: Using questionnaires describing each scale, mothers reported GMFCS, MACS, and CFCS levels in 222…

Apparent chlorofluorocarbon age of ground water of the shallow aquifer system, Naval Weapons Station Yorktown, Yorktown, Virginia

USGS Publications Warehouse

Nelms, David L.; Harlow, George E.; Brockman, Allen R.

2001-01-01

Apparent ages of ground water are useful in the analysis of various components of flow systems, and results of this analysis can be incorporated into investigations of potential pathways of contaminant transport. This report presents the results of a study in 1997 by the U.S. Geological Survey (USGS), in cooperation with the Naval Weapons Station Yorktown, Base Civil Engineer, Environmental Directorate, to describe the apparent age of ground water of the shallow aquifer system at the Station. Chlorofluorocarbons (CFCs), tritium (3H), dissolved gases, stable isotopes, and water-quality field properties were measured in samples from 14 wells and 16 springs on the Station in March 1997.Nitrogen-argon recharge temperatures range from 5.9°C to 17.3°C with a median temperature of 10.9°C, which indicates that ground-water recharge predominantly occurs in the cold months of the year. Concentrations of excess air vary depending upon geohydrologic setting (recharge and discharge areas). Apparent ground-water ages using a CFC-based dating technique range from 1 to 48 years with a median age of 10 years. The oldest apparent CFC ages occur in the upper parts of the Yorktown-Eastover aquifer, whereas the youngest apparent ages occur in the Columbia aquifer and the upper parts of the discharge area setting, especially springs. The vertical distribution of apparent CFC ages indicates that groundwater movement between aquifers is somewhat retarded by the leaky confining units, but the elapsed time is relatively short (generally less than 35 years), as evidenced by the presence of CFCs at depth. The identification of binary mixtures by CFC-based dating indicates that convergence of flow lines occurs not only at the actual point of discharge, but also in the subsurface.The CFC-based recharge dates are consistent with expected 3H concentrations measured in the water samples from the Station. The concentration of 3H in ground water ranges from below the USGS laboratory minimum reporting limit of 0.3 to 15.9 tritium units (TU) with a median value of 10.8 TU. Water-quality field properties are highly variable for ground water with apparent CFC ages less than 15 years because of geochemical processes within local flow systems. Ground water with apparent CFC ages greater than 15 years represents more stable conditions in subregional flow systems.The range of apparent CFC ages is slightly greater than the ranges in time of travel of ground water calculated for shallow wells (less than 60- feet deep) from flow-path analysis. Calculated travel times to springs can be up to two orders of magnitude greater than the CFC-based apparent ages. Reasonable assumptions of values for hydraulic parameters can result in substantial overestimates for time of travel to springs.Recharge rates computed from apparent CFC ages range from 0.29 to 0.89 feet per year (ft/ yr) with an average value of 0.54 ft/yr. The analysis of apparent CFC ages in conjunction with geohydrologic data indicates that young water (less than 50 years) is present at depth (nearly 120 feet) and that both local and subregional flow systems occur in the shallow aquifer system at the Station. The addition of the dimension of time to the three-dimensional framework of Brockman and others (1997) will benefit current (2001) and future remediation activities by providing estimates of advective transport rates and how these rates vary depending upon geohydrologic setting and position within the ground-water-flow system. Estimated ground-water apparent ages and recharge rates can be used as calibration criteria in simulations of ground-water flow on the Station to refine and constrain future ground-water-flow models of the shallow aquifer system.

Greenhouse effect due to chlorofluorocarbons - Climatic implications

NASA Technical Reports Server (NTRS)

Ramanathan, V.

1975-01-01

The infrared bands of chlorofluorocarbons and chlorocarbons enhance the atmospheric greenhouse effect. This enhancement may lead to an appreciable increase in the global surface temperature if the atmospheric concentrations of these compounds reach values of the order of 2 parts per billion.

CONTROL TECHNOLOGY OVERVIEW REPORT: CFC (CHLOROFLUOROCARBON) EMISSIONS FROM RIGID FOAM MANUFACTURING

EPA Science Inventory

The report estimates total chlorofluorocarbon (CFC) emissions from the various rigid foam manufacturing processes and from the foam products themselves, and examines potential methods for reducing these emissions. Options studied include replacement of CFC-blown products with alt...

Consideration of immediate and future consequences, smoking status, and body mass index.

PubMed

Adams, Jean

2012-03-01

Health-related behaviors often involve immediate costs to achieve long-term benefits. How one considers the future outcomes of present day behaviors (e.g., temporal orientation) may play a role in engagement in healthy behaviors. The Consideration of Future Consequences Scale (CFCS) measures temporal orientation on a unidimensional continuum. Recently, 2 subscales of the CFCS have been reported: immediate (CFC-I) and future (CFC-F) consequences. These support a multidimensional conceptualization of temporal orientation. Confirmatory factor analysis was performed on CFCS data. The associations between 2 health-related variables [smoking and body mass index (BMI)] and each subscale were then explored, controlling for sociodemographic variables. A random sample of 2,000 individuals aged 18 years or over was selected from the edited electoral role for one English city and sent a postal questionnaire, including the CFCS and questions on age, gender, socioeconomic position, and self-reported current smoking status and BMI. Complete data was provided by 800 participants (response rate = 40.0%). The 2-factor model fitted CFCS data better than the 1-factor model. In multiple linear regression, CFC-I was positively associated with BMI, B (95% confidence interval [CI]) = 0.47 (0.06 to 0.88), p = .025; and odds of being a current smoker, odds ratio (95% CI) = 1.28 (1.02 to 1.60), p = .035; CFC-F was not associated with health-related variables. These data support the multidimensional conceptualization of temporal orientation. Consideration of immediate consequences may be a more important determinant of health-related behaviors than consideration of future consequences.

Developing and Validating the Communication Function Classification System for Individuals with Cerebral Palsy

ERIC Educational Resources Information Center

Hidecker, Mary Jo Cooley; Paneth, Nigel; Rosenbaum, Peter L.; Kent, Raymond D.; Lillie, Janet; Eulenberg, John B.; Chester, Ken, Jr.; Johnson, Brenda; Michalsen, Lauren; Evatt, Morgan; Taylor, Kara

2011-01-01

Aim: The purpose of this study was to create and validate the Communication Function Classification System (CFCS) for children with cerebral palsy (CP), for use by a wide variety of individuals who are interested in CP. This paper reports the content validity, interrater reliability, and test-retest reliability of the CFCS for children with CP.…

Next Generation Sequencing Approach in a Prenatal Case of Cardio-Facio-Cutaneus Syndrome.

PubMed

Mucciolo, Mafalda; Dello Russo, Claudio; D'Emidio, Laura; Mesoraca, Alvaro; Giorlandino, Claudio

2016-06-16

Cardiofaciocutaneous syndrome (CFCS) belongs to a group of developmental disorders due to defects in the Ras/Mitogen-Activated Protein Kinase (RAS/MAPK) signaling pathway named RASophaties. While postnatal presentation of these disorders is well known, the prenatal and neonatal characteristics are less recognized. Noonan syndrome, Costello syndrome, and CFCS diagnosis should be considered in pregnancies with a normal karyotype and in the case of ultrasound findings such as increased nuchal translucency, polyhydramnios, macrosomia and cardiac defect. Because all the RASopathies share similar clinical features, their molecular characterization is complex, time consuming and expensive. Here we report a case of CFCS prenatally diagnosed through Next Generation Prenatal Diagnosis (NGPD), a new targeted approach that allows us to concurrently investigate all the genes involved in the RASophaties.

Next Generation Sequencing Approach in a Prenatal Case of Cardio-Facio-Cutaneus Syndrome

PubMed Central

Mucciolo, Mafalda; Dello Russo, Claudio; D’Emidio, Laura; Mesoraca, Alvaro; Giorlandino, Claudio

2016-01-01

Cardiofaciocutaneous syndrome (CFCS) belongs to a group of developmental disorders due to defects in the Ras/Mitogen-Activated Protein Kinase (RAS/MAPK) signaling pathway named RASophaties. While postnatal presentation of these disorders is well known, the prenatal and neonatal characteristics are less recognized. Noonan syndrome, Costello syndrome, and CFCS diagnosis should be considered in pregnancies with a normal karyotype and in the case of ultrasound findings such as increased nuchal translucency, polyhydramnios, macrosomia and cardiac defect. Because all the RASopathies share similar clinical features, their molecular characterization is complex, time consuming and expensive. Here we report a case of CFCS prenatally diagnosed through Next Generation Prenatal Diagnosis (NGPD), a new targeted approach that allows us to concurrently investigate all the genes involved in the RASophaties. PMID:27322245

21 CFR 801.433 - Warning statements for prescription and restricted device products containing or manufactured...

Code of Federal Regulations, 2013 CFR

2013-04-01

... device products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances... chlorofluorocarbons or other ozone-depleting substances. (a)(1) All prescription and restricted device products... environment by destroying ozone in the upper atmosphere. (2) The warning statement shall be clearly legible...

21 CFR 801.433 - Warning statements for prescription and restricted device products containing or manufactured...

Code of Federal Regulations, 2010 CFR

2010-04-01

... device products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances... chlorofluorocarbons or other ozone-depleting substances. (a)(1) All prescription and restricted device products... environment by destroying ozone in the upper atmosphere. (2) The warning statement shall be clearly legible...

21 CFR 801.433 - Warning statements for prescription and restricted device products containing or manufactured...

Code of Federal Regulations, 2012 CFR

2012-04-01

... device products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances... chlorofluorocarbons or other ozone-depleting substances. (a)(1) All prescription and restricted device products... environment by destroying ozone in the upper atmosphere. (2) The warning statement shall be clearly legible...

21 CFR 801.433 - Warning statements for prescription and restricted device products containing or manufactured...

Code of Federal Regulations, 2014 CFR

2014-04-01

... device products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances... chlorofluorocarbons or other ozone-depleting substances. (a)(1) All prescription and restricted device products... environment by destroying ozone in the upper atmosphere. (2) The warning statement shall be clearly legible...

21 CFR 801.433 - Warning statements for prescription and restricted device products containing or manufactured...

Code of Federal Regulations, 2011 CFR

2011-04-01

... device products containing or manufactured with chlorofluorocarbons or other ozone-depleting substances... chlorofluorocarbons or other ozone-depleting substances. (a)(1) All prescription and restricted device products... environment by destroying ozone in the upper atmosphere. (2) The warning statement shall be clearly legible...

Chemical evolution of groundwater near a sinkhole lake, northern Florida: 1. Flow patterns, age of groundwater, and influence of lakewater leakage

USGS Publications Warehouse

Katz, Brian G.; Lee, Terrie M.; Plummer, Niel; Busenberg, Eurybiades

1995-01-01

Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC-11, CCl3F; CFC-12, CCl2F2; and CFC-113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11–67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic-rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC-modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC-modeled recharge dates (based on CFC-12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC-modeled recharge dates based on CFC-11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC-12 modeled recharge dates and Darcy's law, were 0.17, 0.033, and 0.019 m/d for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three-dimensional groundwater flow model for transient and steady state flow conditions.

Groundwater Quality, Age, and Probability of Contamination, Eagle River Watershed Valley-Fill Aquifer, North-Central Colorado, 2006-2007

USGS Publications Warehouse

Rupert, Michael G.; Plummer, Niel

2009-01-01

The Eagle River watershed is located near the destination resort town of Vail, Colorado. The area has a fastgrowing permanent population, and the resort industry is rapidly expanding. A large percentage of the land undergoing development to support that growth overlies the Eagle River watershed valley-fill aquifer (ERWVFA), which likely has a high predisposition to groundwater contamination. As development continues, local organizations need tools to evaluate potential land-development effects on ground- and surface-water resources so that informed land-use and water management decisions can be made. To help develop these tools, the U.S. Geological Survey (USGS), in cooperation with Eagle County, the Eagle River Water and Sanitation District, the Town of Eagle, the Town of Gypsum, and the Upper Eagle Regional Water Authority, conducted a study in 2006-2007 of the groundwater quality, age, and probability of contamination in the ERWVFA, north-central Colorado. Ground- and surface-water quality samples were analyzed for major ions, nutrients, stable isotopes of hydrogen and oxygen in water, tritium, dissolved gases, chlorofluorocarbons (CFCs), and volatile organic compounds (VOCs) determined with very low-level laboratory methods. The major-ion data indicate that groundwaters in the ERWVFA can be classified into two major groups: groundwater that was recharged by infiltration of surface water, and groundwater that had less immediate recharge from surface water and had elevated sulfate concentrations. Sulfate concentrations exceeded the USEPA National Secondary Drinking Water Regulations (250 milligrams per liter) in many wells near Eagle, Gypsum, and Dotsero. The predominant source of sulfate to groundwater in the Eagle River watershed is the Eagle Valley Evaporite, which is a gypsum deposit of Pennsylvanian age located predominantly in the western one-half of Eagle County.

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 1. Flow Patterns, Age of Groundwater, and Influence of Lake Water Leakage

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Lee, Terrie M.; Plummer, L. Niel; Busenberg, Eurybiades

1995-06-01

Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC-11, CCl3F; CFC-12, CCl2F2; and CFC-113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11-67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic-rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC-modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC-modeled recharge dates (based on CFC-12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC-modeled recharge dates based on CFC-11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC-12 modeled recharge dates and Darcy's law, were 0.17, 0.033, and 0.019 m/d for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three-dimensional groundwater flow model for transient and steady state flow conditions.

Magnetic hysterysis evolution of Ni-Al alloy with Fe and Mn substitution by vacuum arc melting to produce the room temperature magnetocaloric effect material

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

Notonegoro, Hamdan Akbar; Mechanical Engineering Dept., FT-Universitas Sultan Ageng Tirtayasa, Cilegon 42435; Kurniawan, Budhy

The development of magnetocaloric effect (MCE) material is done in order to reduce the damage of the ozone layer caused by the chlorofluorocarbons (CFCs) emitted into the air. The research dealing with synthesis of magnetocaloric materials based of Ni-Al Heusler Alloy structure and by varying substitution some atoms of Ni with Fe and Al with Mn on Ni-Al Heusler Alloy structure to become Ni{sub 44}Fe{sub 6}Mn{sub 32}Al{sub 18}. Vacuum Arc Melting (VAM) equipment is used to form the alloys on vacuum condition and by flowing argon gas atmosphere and then followed by annealing process for 72 hours. X-Ray Diffraction (XRD)more » reveals that crystallite structure of material is observed. We define that Ni{sub 44}Fe{sub 6} as X{sub 2}, Mn{sub 25} as Y, and Al{sub 18}Mn{sub 7} as Z. Based on the XRD result, we observed that the general formula X{sub 2}YZ is not changed. The PERMAGRAF measurement revealed that there exists of magnetic hysterysis. The hysterysis show that the magnetic structures of the system undego evolution from diamagnetic to soft ferromagnetic material which all of the compound have the same crystallite structure. This evolution indicated that the change in the composition has led to changes the magnetic composition. Mn is the major element that gives strong magnetic properties to the sample. When Mn partially replaced position of Al, the sample became dominant to be influenced to improve their magnetic properties. In addition, substitution a part of Ni by Fe in the composition reveals a pinning of the domain walls in the sample.« less

A Model-Based Evaluation of the Inverse Gaussian Transit-Time Distribution Method for Inferring Anthropogenic Carbon Storage in the Ocean

NASA Astrophysics Data System (ADS)

He, Yan-Chun; Tjiputra, Jerry; Langehaug, Helene R.; Jeansson, Emil; Gao, Yongqi; Schwinger, Jörg; Olsen, Are

2018-03-01

The Inverse Gaussian approximation of transit time distribution method (IG-TTD) is widely used to infer the anthropogenic carbon (Cant) concentration in the ocean from measurements of transient tracers such as chlorofluorocarbons (CFCs) and sulfur hexafluoride (SF6). Its accuracy relies on the validity of several assumptions, notably (i) a steady state ocean circulation, (ii) a prescribed age tracer saturation history, e.g., a constant 100% saturation, (iii) a prescribed constant degree of mixing in the ocean, (iv) a constant surface ocean air-sea CO2 disequilibrium with time, and (v) that preformed alkalinity can be sufficiently estimated by salinity or salinity and temperature. Here, these assumptions are evaluated using simulated "model-truth" of Cant. The results give the IG-TTD method a range of uncertainty from 7.8% to 13.6% (11.4 Pg C to 19.8 Pg C) due to above assumptions, which is about half of the uncertainty derived in previous model studies. Assumptions (ii), (iv) and (iii) are the three largest sources of uncertainties, accounting for 5.5%, 3.8% and 3.0%, respectively, while assumptions (i) and (v) only contribute about 0.6% and 0.7%. Regionally, the Southern Ocean contributes the largest uncertainty, of 7.8%, while the North Atlantic contributes about 1.3%. Our findings demonstrate that spatial-dependency of Δ/Γ, and temporal changes in tracer saturation and air-sea CO2 disequilibrium have strong compensating effect on the estimated Cant. The values of these parameters should be quantified to reduce the uncertainty of IG-TTD; this is increasingly important under a changing ocean climate.

Total environmental warming impact (TEWI) calculations for alternative automative air-conditioning systems

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

Sand, J.R.; Fischer, S.K.

1997-01-01

The Montreal Protocol phase-out of chlorofluorocarbons (CFCs) has required manufacturers to develop refrigeration and air-conditioning systems that use refrigerants that can not damage stratospheric ozone. Most refrigeration industries have adapted their designs to use hydrochlorofluorocarbon (HCFC) or hydrofluorocarbon (HFC) refrigerants; new automobile air- conditioning systems use HFC-134a. These industries are now being affected by scientific investigations of greenhouse warming and questions about the effects of refrigerants on global warming. Automobile air-conditioning has three separate impacts on global warming; (1) the effects of refrigerant inadvertently released to the atmosphere from accidents, servicing, and leakage; (2) the efficiency of the cooling equipmentmore » (due to the emission of C0{sub 2} from burning fuel to power the system); and (3) the emission of C0{sub 2} from burning fuel to transport the system. The Total Equivalent Warming Impact (TEWI) is an index that should be used to compare the global warming effects of alternative air-conditioning systems because it includes these contributions from the refrigerant, cooling efficiency, and weight. This paper compares the TEWI of current air-conditioning systems using HFC-134a with that of transcritical vapor compression system using carbon dioxide and systems using flammable refrigerants with secondary heat transfer loops. Results are found to depend on both climate and projected efficiency of C0{sub 2}systems. Performance data on manufacturing prototype systems are needed to verify the potential reductions in TEWI. Extensive field testing is also required to determine the performance, reliability, and ``serviceability`` of each alternative to HFC-134a to establish whether the potential reduction of TEWI can be achieved in a viable consumer product.« less

Rapid Reconnaissance Mapping of Volatile Organic Compounds by Photoionization Detection at the USGS Amargosa Desert Research Site

NASA Astrophysics Data System (ADS)

Thordsen, J. J.; Stonestrom, D. A.; Conaway, C. H.; Luo, W.; Baker, R. J.; Andraski, B. J.

2015-12-01

Two types of handheld photoionization detectors were evaluated in April 2015 for reconnaissance mapping of volatile organic compounds (VOCs) in the unsaturated zone surrounding legacy disposal trenches for commercial low-level radioactive waste near Beatty, Nevada (USA). This method is rapid and cost effective when compared to the more conventional procedure used ate the site, where VOCs are collected on sorbent cartridges in the field followed by thermal desorption, gas chromatographic separation, and quantitation by mass spectroscopy in the laboratory (TD-GC-MS analysis). Using the conventional method, more than sixty distinct compounds have been identified in the 110-m deep unsaturated zone vapor phase, and the changing nature of the VOC mix over a 15-yr timeframe has been recorded. Analyses to date have identified chlorofluorocarbons (CFCs), chlorinated ethenes, chlorinated ethanes, gasoline-range hydrocarbons, chloroform, and carbon tetrachloride as the main classes of VOCs present. The VOC plumes emanating from the various subgroups of trenches are characterized by different relative abundances of the compound classes, and total VOC concentrations that cover several orders of magnitude. One of the photoionization detectors, designed for industrial compliance testing, lacked sufficient dynamic range and sensitivity to be useful. The other, a wide range (1 ppb-20,000 ppm) research-grade instrument with a 10.6 eV photoionization detector (PID) lamp, produced promising results, detecting roughly half of the non-CFC VOCs present. The rapid and inexpensive photoionization method is envisioned as a screening tool to supplement, expedite, and direct the collection of additional samples for TD-GC-MS analyses at this and other VOC-contaminated sites.

Influence of fracture anisotropy on ground water ages and chemistry, Valley and Ridge province, Pennsylvania

USGS Publications Warehouse

Burton, W.C.; Plummer, Niel; Busenberg, E.; Lindsey, B.D.; Gburek, W.J.

2002-01-01

Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3H/3He) data were obtained from two arrays of nested piezometers located on the north limb of an anticline in fractured sedimentary rocks in the Valley and Ridge geologic province of Pennsylvania. The fracture geometry of the gently east plunging fold is very regular and consists predominately of south dipping to subhorizontal to north dipping bedding-plane parting and east striking, steeply dipping axial-plane spaced cleavage. In the area of the piezometer arrays, which trend north-south on the north limb of the fold, north dipping bedding-plane parting is a more dominant fracture set than is steeply south dipping axial-plane cleavage. The dating of ground water from the piezometer arrays reveals that ground water traveling along paths parallel to the dip direction of bedding-plane parting has younger 3H/3He and CFC model ages, or a greater component of young water, than does ground water traveling along paths opposite to the dip direction. In predominantly unmixed samples there is a strong positive correlation between age of the young fraction of water and dissolved sodium concentration. The travel times inferred from the model ages are significantly longer than those previously calculated by a ground water flow model, which assumed isotropically fractured layers parallel to topography. A revised model factors in the directional anisotropy to produce longer travel times. Ground water travel times in the watershed therefore appear to be more influenced by anisotropic fracture geometry than previously realized. This could have significant implications for ground water models in other areas underlain by similarly tilted or folded sedimentary rock, such as elsewhere in the Valley and Ridge or the early Mesozoic basins.

Prediction and assessment of flammability hazards associated with metered-dose inhalers containing flammable propellants.

PubMed

Dalby, R N

1992-05-01

Several potential replacements for chlorofluorocarbons (CFCs) in metered-dose inhalers (MDIs) are flammable. The flammability hazard associated with their use was assessed using a range of MDIs containing 0-100% (w/w) n-butane (flammable) in HFC-134a (non-flammable) fitted with either 25-, 63-, or 100-microliters metering valves or continuous valves. In flame projection tests each MDI was fired horizontally into a flame, and the ignited flume length emitted from the MDI was measured. Flame projections of greater than or equal to 60 cm were produced by all formulations fitted with continuous valves which contained greater than or equal to 40% (w/w) n-butane in HFC-134a. Using metering valves the maximum flame projection obtained was 30 cm. This was observed with a formulation containing 90% (w/w) n-butane in HFC-134a and a 100-microliters valve. For a particular formulation, smaller metering valves produced shorter flame projections. Because many MDIs are used in conjunction with extension devices, the likelihood of accidental propellant vapor ignition was determined in Nebuhaler and Inspirease reservoirs and a Breathancer spacer. Ignition was predictable based on propellant composition, metered volume, number of actuations, and spacer capacity. Calculated n-butane concentrations in excess of the lower flammability limit [LFL; 1.9% (v/v)] but below the upper flammability limit [UFL; 8.5% (v/v)] were usually predictive of flammability following ignition by a glowing nichrome wire mounted inside the extension device. No ignition was predicted or observed following one or two 25-microliters actuations of 100% n-butane into large volume Nebuhaler (750 ml) or Inspirease (660 ml) devices.(ABSTRACT TRUNCATED AT 250 WORDS)

Oxygen anion (O- ) and hydroxide anion (HO- ) reactivity with a series of old and new refrigerants.

PubMed

Le Vot, Clotilde; Lemaire, Joël; Pernot, Pascal; Heninger, Michel; Mestdagh, Hélène; Louarn, Essyllt

2018-04-01

The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O - is formed by dissociative electron attachment to N 2 O and HO - by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H 2 + transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O - and HO - as chemical ionization reagents for trace analysis is discussed. Copyright © 2017 John Wiley & Sons, Ltd.

Health Assessment Document for 1,1,2-Trichloro-1,2,2-Trifluoroethane (Chlorofluorocarbon CFC-113)

EPA Science Inventory

Chlorofluorocarbon 113 (1,1,2-trichloro-1,2,2,-trifluoroethane) has little potential to cause direct adverse health effects at levels found or expected in the general environment (<4.2 ppb). Experimental data do not indicate adverse health effects in humans at a TLV of 1,000 ppm....

Systemic exposure and urinary cortisol effects of fluticasone propionate formulated with hydrofluoroalkane in 4- to 11-year-olds with asthma.

PubMed

Kim, Kenneth T; Milgrom, Henry; Yoon, Y Kellie; Levy, Arden L; Matz, Paul; Welch, Michael J; Cahn, Anthony; Collins, David A; Kathman, Steven; Mehta, Rashmi; Su, Sheng-Fang; Kunka, Robert L

2008-01-01

The systemic exposure of fluticasone propionate with hydrofluoroalkane propellant compared with chlorofluoro-carbon propellant and the effect of fluticasone propionate hydrofluoroalkane on 24-hour urinary cortisol in children aged 4 to 11 years with asthma were evaluated. Study 1 was an open-label, 2-way crossover study in which 16 subjects were randomized to 7.5 days each of fluticasone propionate hydrofluoroalkane 88 mug twice a day or fluticasone propionate chlorofluorocarbon 88 mug twice a day. In study 2, 63 subjects received 13.5 days of placebo followed by 27.5 days of fluticasone propionate hydrofluoroalkane 88 mug twice a day. The main outcome measure for study 1 was the difference between fluticasone propionate hydrofluoroalkane and fluticasone propionate chlorofluorocarbon in fluticasone propionate AUC(last) (area under the plasma fluticasone propionate concentration-time curve from zero up to the last quantifiable plasma concentration), and for study 2, 24-hour overnight urinary cortisol excretion. In study 1, fluticasone propionate systemic exposure was significantly lower (55%) with hydrofluoroalkane metered dose inhaler compared with chlorofluorocarbon metered dose inhaler. Study 2 showed no statistically significant changes in 24-hour overnight urinary cortisol excretion and no relationship to fluticasone propionate systemic exposure at this dose. The results of these 2 studies showed that in children aged 4 to 11 years with asthma, fluticasone propionate hydrofluoroalkane has lower systemic exposure compared with chlorofluorocarbon and no hypothalamic-pituitary-adrenal axis effects as measured by 24-hour urinary cortisol excretion.

A United States regulator's perspective on the ongoing chlorofluorocarbon transition.

PubMed

Meyer, R J

1999-12-01

The Food and Drug Administration (FDA) put in place a general ban on the use of chlorofluorocarbons for the products it regulates (medical devices, drugs, and foods) in 1978, exempting those products where chlorofluorocarbon use was determined to be essential for the public health. In the intervening years, as the international commitment to a full transition away from all chlorofluorocarbon use took shape under the Montreal Protocol, the FDA has worked with industry to facilitate the development and testing of alternative technologies and products for inhalation drug products. As these alternative products begin to move from testing through the approval process and into marketing, the FDA is working collaboratively with the Environmental Protection Agency, other governmental agencies, and nongovernmental stakeholders to develop a transition policy for the United States. The transition policy for metered dose inhalers must be one that achieves the dual aims of first protecting the patients who rely on these vital medical products, while also achieving the public health need of protecting the ozone layer. As a part of developing such a transition strategy, the FDA published an advance notice of proposed rulemaking (ANPRM) in March 1997. The ANPRM proposed mechanisms by which the FDA could determine when chlorofluorocarbon use in a drug product could no longer be considered essential. The ANPRM resulted in a large amount of valuable public debate and input. The FDA is now working to incorporate the knowledge gained from these public comments as it continues the rule-making process.

Back to "the Future": Evidence of a Bifactor Solution for Scores on the Consideration of Future Consequences Scale.

PubMed

McKay, Michael T; Morgan, Grant B; van Exel, N Job; Worrell, Frank C

2015-01-01

Despite its widespread use, disagreement remains regarding the structure of the Consideration of Future Consequences Scale (CFCS). In particular there is disagreement regarding whether the scale assesses future orientation as a unidimensional or multidimensional (immediate and future) construct. Using 2 samples of high school students in the United Kingdom, 4 models were tested. The totality of results including item loadings, goodness-of-fit indexes, and reliability estimates all supported the bifactor model, suggesting that the 2 hypothesized factors are better understood as grouping or method factors rather than as representative of latent constructs. Accordingly this study supports the unidimensionality of the CFCS and the scoring of all 12 items to produce a global future orientation score. Researchers intending to use the CFCS, and those with existing data, are encouraged to examine a bifactor solution for the scale.

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 trends of tropospheric hydroxyl radicals (OH) from the rates of destruction of atmospheric trichloroethane (CH3CCl3), HFCs, and HCFCs and estimates of their emissions; (5) to determine from atmospheric observations and estimates of their destruction rates the magnitudes and distributions by region of surface sources and sinks of all measured gases; (6) to provide accurate data on the global accumulation of many of these trace gases that are used to test the synoptic-, regional-, and global-scale circulations predicted by three-dimensional models; and (7) to provide global and regional measurements of methane, carbon monoxide, and molecular hydrogen and estimates of hydroxyl levels to test primary atmospheric oxidation pathways at midlatitudes and the tropics. Network Information and Data Repository: http://agage.mit.edu/data or http://cdiac.ess-dive.lbl.gov/ndps/alegage.html (https://doi.org/10.3334/CDIAC/atg.db1001).

Estimates of tracer-based piston-flow ages of groundwater from selected sites-National Water-Quality Assessment Program, 1992-2005

USGS Publications Warehouse

Hinkle, Stephen R.; Shapiro, Stephanie D.; Plummer, Niel; Busenberg, Eurybiades; Widman, Peggy K.; Casile, Gerolamo C.; Wayland, Julian E.

2011-01-01

This report documents selected age data interpreted from measured concentrations of environmental tracers in groundwater from 1,399 National Water-Quality Assessment (NAWQA) Program groundwater sites across the United States. The tracers of interest were chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), and tritium/helium-3 (3H/3He). Tracer data compiled for this analysis primarily were from wells representing two types of NAWQA groundwater studies - Land-Use Studies (shallow wells, usually monitoring wells, in recharge areas under dominant land-use settings) and Major-Aquifer Studies (wells, usually domestic supply wells, in principal aquifers and representing the shallow, used resource). Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) associated with Land-Use Studies also were included. Tracer samples were collected between 1992 and 2005, although two networks sampled from 2006 to 2007 were included because of network-specific needs. Tracer data from other NAWQA Program components (Flow System Studies, which are assessments of processes and trends along groundwater flow paths, and various topical studies) were not compiled herein. Tracer data from NAWQA Land-Use Studies and Major-Aquifer Studies that previously had been interpreted and published are compiled herein (as piston-flow ages), but have not been reinterpreted. Tracer data that previously had not been interpreted and published are evaluated using documented methods and compiled with aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF6), estimates of tracer-based piston-flow ages, and selected ancillary data, such as redox indicators, well construction, and major dissolved gases (N2, O2, Ar, CH4, and CO2). Tracer-based piston-flow ages documented in this report are simplistic representations of the tracer data. Tracer-based piston-flow ages are a convenient means of conceptualizing groundwater age. However, the piston-flow model is based on the potentially limiting assumptions that tracer transport is advective and that no mixing occurs. Additional uncertainties can arise from tracer degradation, sorption, contamination, or fractionation; terrigenic (natural) sources of tracers; spatially variable atmospheric tracer concentrations; and incomplete understanding of mechanisms of recharge or of the conditions under which atmospheric tracers were partitioned to recharge. The effects of some of these uncertainties are considered herein. For example, degradation, contamination, or fractionation often can be identified or inferred. However, detailed analysis of the effects of such uncertainties on the tracer-based piston-flow ages is constrained by sparse data and an absence of complementary lines of evidence, such as detailed solute transport simulations. Thus, the tracer-based piston-flow ages compiled in this report represent only an initial interpretation of the tracer data.

Health Assessment Document for 1,1,2-Trichloro-1,2,2-Trifluoroethane (Chlorofluorocarbon CFC-113)(Revised External Review Draft)

EPA Science Inventory

Chlorofluorocarbon 113 (1,1,2-trichloro-1,2,2-trifluoroethane) has little potential to cause direct adverse health effects at levels found or expected in the general environment (<4.2 ppb). Experimental data do not indicate adverse health effects in humans at a TLV of 1,000 ppm. ...

Evaluating Potential Bias in Media Coverage of the Public Debate over Acid Rain and Chlorofluorocarbons in the 1980s

ERIC Educational Resources Information Center

Williams, Tiffany Dawn; Moore, Rebecca; Markewitz, Daniel

2012-01-01

This study evaluates media coverage of two important environmental issues from the 1980s (acid rain and chlorofluorocarbons), providing historical context for current media coverage analysis. Focusing on popular magazine articles, this study identifies key characteristics of content and presentation. Content-related characteristics are inclusion…

Using Simple Linear Regression to Assess the Success of the Montreal Protocol in Reducing Atmospheric Chlorofluorocarbons

ERIC Educational Resources Information Center

Nelson, Dean

2009-01-01

Following the Guidelines for Assessment and Instruction in Statistics Education (GAISE) recommendation to use real data, an example is presented in which simple linear regression is used to evaluate the effect of the Montreal Protocol on atmospheric concentration of chlorofluorocarbons. This simple set of data, obtained from a public archive, can…

Perinatal features of the RASopathies: Noonan syndrome, cardiofaciocutaneous syndrome and Costello syndrome.

PubMed

Myers, Angela; Bernstein, Jonathan A; Brennan, Marie-Luise; Curry, Cynthia; Esplin, Edward D; Fisher, Jamie; Homeyer, Margaret; Manning, Melanie A; Muller, Eric A; Niemi, Anna-Kaisa; Seaver, Laurie H; Hintz, Susan R; Hudgins, Louanne

2014-11-01

The RASopathies are a family of developmental disorders caused by heritable defects of the RAS/MAPK signaling pathway. While the postnatal presentation of this group of disorders is well known, the prenatal and neonatal findings are less widely recognized. We report on the perinatal presentation of 10 patients with Noonan syndrome (NS), nine with Cardiofaciocutaneous syndrome (CFCS) and three with Costello syndrome (CS), in conjunction with the results of a comprehensive literature review. The majority of perinatal findings in NS, CS, and CFCS are shared: polyhydramnios; prematurity; lymphatic dysplasia; macrosomia; relative macrocephaly; respiratory distress; hypotonia, as well as cardiac and renal anomalies. In contrast, fetal arrhythmia and neonatal hypoglycemia are relatively specific to CS. NS, CS, and CFCS should all be considered as a possible diagnosis in pregnancies with a normal karyotype and ultrasound findings of a RASopathy. Recognition of the common perinatal findings of these disorders should facilitate both their prenatal and neonatal diagnosis. © 2014 Wiley Periodicals, Inc.

The family needs of parents of preschool children with cerebral palsy: the impact of child's gross motor and communications functions.

PubMed

Bertule, Dace; Vetra, Anita

2014-01-01

An understanding of the needs of families of preschool children with cerebral palsy (CP) is of essential importance if efficient and cost-effective services are to be provided to them. The aims of this study were to identify the most frequently expressed needs of families with preschool children with CP; differences in the amount and types of family needs based on the child's gross motor function and communication function level; and the impact of the child's gross motor function and communication function level on the type and amount of family needs. A total of 227 parents of preschool children with CP completed a modified version of the Family Needs Survey and a demographic questionnaire. Children's gross motor function level and communication function level was classified using the Gross Motor Function Classification System (GMFCS) and the Communication Function Classification System (CFCS), respectively. The total number of family needs differed based on GMFCS and CFCS levels. Children's GMFCS and CFCS level were not significant predictors of overall family needs (adjusted R(2)=0.163). In this model the GMFCS level of children did not account for the total number of family needs, while the CFCS level did. Child's limitations in terms of communication and gross motor functions must be taken into consideration when planning services for families with preschool children with CP. Copyright © 2014 Lithuanian University of Health Sciences. Production and hosting by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Trospospheric degradation chemistry of HCFC-123 (CF 3CHCl 2): A proposed replacement chlorofluorocarbon

NASA Astrophysics Data System (ADS)

Hayman, G. D.; Jenkin, M. E.; Murrells, T. P.; Johnson, C. E.

HCFC-123 has been proposed as a replacement for some of the fully halogenated chlorofluorocarbons and other chlorinated hydrocarbons, which are being phased out under the Montreal Protocol. This paper reports laboratory studies which were undertaken to determine kinetic and mechanistic parameters of reactions involved in the atmospheric degradation of HCFC-123 and the use of these parameters in a 2D global model of the troposphere to evaluate the yields of products formed in the degradation. The experimental studies have made use of the laser flash photolysis technique with time-resolved ultra-violet absorption spectroscopy for the kinetic measurements and broad-band ultra-violet absorption spectroscopy for product characterization. Rate coefficients have been determined for the self-reaction of CF 3CCl 2O 2 as (3.6±0.5)×10 -12 cm 3 mol -1 s -1 and for its reactions with HO 2 and NO as (1.9±0.7)×10 -12 cm 3 mol -1 s -1 and (1.5-2.0)×10 -11 cm 3 mol -1 s -1, respectively, at room temperature. Kinetic data have also been obtained for the reaction of CF 3CCl 2O 2 with C 2H 5O 2 and two channels have been identified; CF 3CCl 2+O 2+C 2H 5O 2→CF 3CCl 2O+C 2H 5O+ C 2H 5O+O 2, k=(9 +9-5)×10 13 cm 3 mol -1 s -1 and CF 3CCl 2O 2+C 2H 5O 2→CF 3CCl 2OH+CH 3CHO+O 2, k=(3.6±0.5)× 10 -12 cm 3 mol -1 s -1. Studies undertaken using the Cl-initiated oxidation of HCFC-123 suggest that trifluoroacetyl chloride, CF 3COCl, is the major product of the gas-phase degradation. The kinetic and mechanistic data have been used to formulate a chemical module of the degradation of HCFC-123 in the trophosphere. The module has been incorporated into a 2D model of the global troposphere so that the potential atmospheric impact of using HCFC-123 can be assessed.

Ten years of continuous observations of stratospheric ozone depleting gases at Monte Cimone (Italy)--comments on the effectiveness of the Montreal Protocol from a regional perspective.

PubMed

Maione, M; Giostra, U; Arduini, J; Furlani, F; Graziosi, F; Lo Vullo, E; Bonasoni, P

2013-02-15

Halogenated gases potentially harmful to the stratospheric ozone layer are monitored worldwide in order to assess compliance with the Montreal Protocol requiring a phase out of these compounds on a global scale. We present the results of long term (2002-2011) continuous observation conducted at the Mt. Cimone GAW Global Station located on the highest peak of the Italian Northern Apennines, at the border of two important regions: the Po Valley (and the Alps) to the North and the Mediterranean Basin to the South. Bi-hourly air samples of CFC-12, CFC-11, CFC-114, CFC-115, H-1211, H-1301, methyl chloroform, carbon tetrachloride, HCFC-22, HCFC-142b, HCFC-124 and methyl bromide are collected and analysed using a gas chromatograph-mass spectrometer, providing multi annual time series. In order to appreciate the effectiveness of the Montreal Protocol from a regional perspective, trends and annual growth rates of halogenated species have been calculated after identification of their baseline values. A comparison with results from other international observation programmes is also presented. Our data show that the peak in the atmospheric mixing ratios of four chlorofluorocarbons, two halons and two chlorocarbons has been reached and all these species now show a negative atmospheric trend. Pollution episodes are still occurring for species like halon-1211, methyl chloroform and carbon tetrachloride, indicating fresh emissions from the site domain which could be ascribed both to fugitive un-reported uses of the compounds and/or emissions from banks. For the hydrofluorocarbons changes in the baseline are affected by emissions from fast developing Countries in East Asia. Fresh emissions from the site domain are clearly declining. Methyl bromide, for which the Mediterranean area is an important source region, shows, in a generally decreasing trend, an emission pattern that is not consistent with the phase-out schedule of this compound, with a renewed increase in the last two years of pollution episodes. Copyright © 2012 Elsevier B.V. All rights reserved.

Functional Communication Profiles in Children with Cerebral Palsy in Relation to Gross Motor Function and Manual and Intellectual Ability.

PubMed

Choi, Ja Young; Park, Jieun; Choi, Yoon Seong; Goh, Yu Ra; Park, Eun Sook

2018-07-01

The aim of the present study was to investigate communication function using classification systems and its association with other functional profiles, including gross motor function, manual ability, intellectual functioning, and brain magnetic resonance imaging (MRI) characteristics in children with cerebral palsy (CP). This study recruited 117 individuals with CP aged from 4 to 16 years. The Communication Function Classification System (CFCS), Viking Speech Scale (VSS), Speech Language Profile Groups (SLPG), Gross Motor Function Classification System (GMFCS), Manual Ability Classification System (MACS), and intellectual functioning were assessed in the children along with brain MRI categorization. Very strong relationships were noted among the VSS, CFCS, and SLPG, although these three communication systems provide complementary information, especially for children with mid-range communication impairment. These three communication classification systems were strongly related with the MACS, but moderately related with the GMFCS. Multiple logistic regression analysis indicated that manual ability and intellectual functioning were significantly related with VSS and CFCS function, whereas only intellectual functioning was significantly related with SLPG functioning in children with CP. Communication function in children with a periventricular white matter lesion (PVWL) varied widely. In the cases with a PVWL, poor functioning was more common on the SLPG, compared to the VSS and CFCS. Very strong relationships were noted among three communication classification systems that are closely related with intellectual ability. Compared to gross motor function, manual ability seemed more closely related with communication function in these children. © Copyright: Yonsei University College of Medicine 2018.

Apparatus Circulates Sterilizing Gas

NASA Technical Reports Server (NTRS)

Cross, John H.; Schwarz, Ray P.

1991-01-01

Apparatus circulates sterilizing gas containing ethylene oxide and chlorofluorocarbon through laboratory or medical equipment. Confines sterilizing gas, circulating it only through parts to be treated. Consists of two units. One delivers ethylene oxide/chlorofluorocarbon gas mixture and removes gas after treatment. Other warms, humidifies, and circulates gas through equipment to be treated. Process provides reliable sterilization with negligible residual toxicity from ethylene oxide. Particularly suitable for sterilization of interiors of bioreactors, heart/lung machines, dialyzers, or other equipment including complicated tubing.

Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies

NASA Astrophysics Data System (ADS)

Hoffmann, Lars; Hoppe, Charlotte; Müller, Rolf; Dutton, Geoffrey S.; Gille, John C.; Griessbach, Sabine; Jones, Ashley; Meyer, Catrin I.; Spang, Reinhold; Volk, C. Michael; Walker, Kaley A.

2015-04-01

Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their stratospheric loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer-tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present new estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 yr for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47 ± 0.08 and a CFC-12 lifetime of 112(96 - 133) yr for ACE-FTS, a ratio of 0.46 ± 0.07 and a lifetime of 113(97 - 134) yr for HIRDLS, and a ratio of 0.46 ± 0.08 and a lifetime of 114(98 - 136) yr for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.46 ± 0.04 and the CFC-12 lifetime estimate is 113(103 - 124) yr. These results are in excellent agreement with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43 - 67) yr for CFC-11 and 102(88 - 122) yr for CFC-12, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled EMAC/CLaMS model we found a CFC-11/CFC-12 lifetime ratio of 0.48 ± 0.07 and a CFC-12 lifetime of 110(95 - 129) yr, based on a ten-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers. Reference: Hoffmann, L., Hoppe, C. M., Müller, R., Dutton, G. S., Gille, J. C., Griessbach, S., Jones, A., Meyer, C. I., Spang, R., Volk, C. M., and Walker, K. A.: Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies, Atmos. Chem. Phys., 14, 12479-12497, doi:10.5194/acp-14-12479-2014, 2014.

Hydrogeologic Investigation, Water Chemistry Analysis, and Model Delineation of contributing Areas for City of Tallahassee Public-Supply Wells, Tallahassee, Florida

USGS Publications Warehouse

Davis, J. Hal; Katz, Brian G.

2007-01-01

Ground water from the Upper Floridan aquifer is the sole source of water supply for Tallahassee, Florida, and the surrounding area. The City of Tallahassee (the City) currently operates 28 water-supply wells; 26 wells are distributed throughout the City and 2 are located in Woodville, Florida. Most of these wells yield an ample supply of potable water; however, water from several wells has low levels of tetrachloroethylene (PCE). The City removes the PCE from the water by passing it through granular-activated carbon units before distribution. To ensure that water-supply wells presently free of contamination remain clean, it is necessary to understand the ground-water flow system in sufficient detail to protect the contributing areas. Ground-water samples collected from four public-supply wells were analyzed for tritium (3H), chlorofluorocarbons (CFCs), and sulfur hexafluoride (SF6). Using data for the CFC compounds, apparent ground-water ages ranged from 7 to 31 years. For SF6, the apparent ages tended to be about 5 to 10 years younger than those from CFCs. Apparent ages based on the tritium/tritiogenic helium-3 (3H/3Hetrit) method ranged from 26 to 33 years. The three dating methods indicate that the apparent age of ground water generally decreases from northern to southern Leon County. This southward trend of decreasing ages is consistent with increasing amounts of recharge that occur as ground water moves from north to south. The ground-water age data derived by geochemical and tracer analyses were used in combination with the flow model and particle tracking to determine an effective porosity for the Hawthorn clays and Upper Floridan aquifer. The effective porosities for the Upper Floridan aquifer that resulted in best model matches were averaged to produce an effective porosity of 7 percent, and the effective porosities for the Hawthorn clays that resulted in a match were averaged to produce an effective porosity of 22 percent. Probabilistic contributing areas were determined for 26 City wells using MODFLOW and MODPATH. For each probabilistic contributing area delineated, the model was run 100 times and the results were analyzed statistically. For each of the 100 runs, a different hydraulic conductivity for each of the zones was assigned to the Upper Floridan aquifer. The hydraulic conductivities were generated randomly assuming a lognormal probability distribution; the mean of the distribution was equal to the hydraulic conductivity from the calibrated model. The 5-year time-dependent capture zones (TDCZs), assuming effective porosities of 0.1, 1, and 7 percent for four representative wells, were delineated. The higher probabilities of capture (greater than 40, 60, and 80 percent) were similar for all effective porosities, and the TDCZ delineated using a 7-percent porosity was slightly smaller; the lower probabilities of capture (greater than 10 and 20 percent) showed a large range of variability.

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...

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

PubMed

Guo, H; Lee, S C; Louie, P K K; Ho, K F

2004-12-01

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas in winter motor vehicle emissions would be the major sources of the carbonyls. The photochemical reactivity of selected VOCs was estimated in this study. The largest contributors to ozone formation were formaldehyde, toluene, propene, m,p-xylene, acetaldehyde, 1-butene/i-butene, isoprene and n-butane, suggesting that motor vehicles, gasoline evaporation, use of solvents, leakage of LPG, photochemical processes and biogenic emission are sources in the production of ozone. On the other hand, VOCs from vehicles and gasoline evaporation were predominant with respect to reactions with OH radical.

Effects of chemically characterized fractions from aerial parts of Echinacea purpurea and E. angustifolia on myelopoiesis in rats.

PubMed

Ramasahayam, Sindhura; Baraka, Hany N; Abdel Bar, Fatma M; Abuasal, Bilal S; Widrlechner, Mark P; Sayed, Khalid A El; Meyer, Sharon A

2011-11-01

Echinacea species are used for beneficial effects on immune function, and various prevalent phytochemicals have immunomodulatory effects. Using a commercial E. purpurea (L.) Moench product, we have evaluated the myelopoietic effect on bone marrow of rats treated with various extracts and correlated this with their chemical class composition. Granulocyte/macrophage-colony forming cells (GM-CFCs) from femurs of female Sprague-Dawley rats were assessed at 24 h after 7 daily oral treatments. A 75% ethanolic extract at 50 mg dried weight (derived from 227 mg aerial parts) per kg body weight increased GM-CFCs by 70% but at 100 mg/kg was without effect. Ethanolic extracts from aerial parts of E. angustifolia DC. var. angustifolia and E. purpurea from the USDA North Central Regional Plant Introduction Station increased GM-CFCs by 3- and 2-fold, respectively, at 200 mg/kg (~1400 mg/kg plant material). Extract from another USDA E. angustifolia was inactive. Proton and APT NMR, MS, and TLC indicated alkylamides and caffeic-acid derivatives (CADs) present in ethanolic extracts of both the commercial and USDA-derived material. Cichoric and caftaric acids were prominent in both E. purpurea ethanolic extracts but absent in E. angustifolia. Aqueous extract of the commercial material exhibited polysaccharide and CAD signatures and was without effect on GM-CFCs. A methanol-CHCl3 fraction of commercial source, also inactive, was almost exclusively 1:4 nonanoic: decanoic acids, which were also abundant in commercial ethanolic extract but absent from USDA material. In conclusion, we have demonstrated an ethanolextractable myelostimulatory activity in Echinacea aerial parts that, when obtained from commercial herbal supplements, may be antagonized by medium-chain fatty acids presumably derived from a non-plant additive. © Georg Thieme Verlag KG Stuttgart · New York.

The mandibular ridge oral mucosa model of stromal influences on the endothelial tip cells: an immunohistochemical and TEM study.

PubMed

Rusu, Mugurel Constantin; Didilescu, Andreea Cristiana; Stănescu, Ruxandra; Pop, Florinel; Mănoiu, Valentina Mariana; Jianu, Adelina Maria; Vâlcu, Marek

2013-02-01

This study aimed to evaluate by immunohistochemistry and transmission electron microscopy (TEM) the morphological features of the oral mucosa endothelial tip cells (ETCs) and to determine the immune and ultrastructural patterns of the stromal nonimmune cells which could influence healing processes. Immune labeling was performed on bioptic samples obtained from six edentulous patients undergoing surgery for dental implants placement; three normal samples were collected from patients prior to the extraction of the third mandibular molar. The antibodies were tested for CD34, CD117(c-kit), platelet derived growth factor receptor-alpha (PDGFR-α), Mast Cell Tryptase, CD44, vimentin, CD45, CD105, alpha-smooth muscle actin, FGF2, Ki67. In light microscopy, while stromal cells (StrCs) of the reparatory and normal oral mucosa, with a fibroblastic appearance, were found positive for a CD34/CD44/CD45/CD105/PDGFR-α/vimentin immune phenotype, the CD117/c-kit labeling led to a positive stromal reaction only in the reparatory mucosa. In TEM, non-immune StrCs presenting particular ultrastructural features were identified as circulating fibrocytes (CFCs). Within the lamina propria CFCs were in close contact with ETCs. Long processes of the ETCs were moniliform, and hook-like collaterals were arising from the dilated segments, suggestive for a different stage migration. Maintenance and healing of oral mucosa are so supported by extensive processes of angiogenesis, guided by ETCs that, in turn, are influenced by the CFCs that populate the stromal compartment both in normal and reparatory states. Therefore, CFCs could be targeted by specific therapies, with pro- or anti-angiogenic purposes. Copyright © 2012 Wiley Periodicals, Inc.

Environmental challenge as a geologist

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

Hanson, B.M.

1994-12-31

Many scientific environmental studies involving geology are now becoming apparent. If we can convince the regulatory agencies to take advantage of our geologic knowledge to assess environmental problems, many unnecessary mandates can be modified. Isn`t it strange that Mt. Erebus in the Antarctic pumps over 1,000 tons of chlorine directly into the vortex of the earth every day and has for over 100 years? Yet man and CFCs (chlorofluorocarbons) are being blamed for the ozone hole and global warming. Recent ice cores have been recovered in Greenland which date back 250,000 years in time. This scientific study indicated that themore » climate in the northern hemisphere has always been cyclic. The United States Geological Survey has recently completed a study of the Exxon Valdes oil spill and has found Monterey oil residues are more prevalent than the North Slope oil. The Monterey oil is present as a result of the 1994 Alaska earthquake. Also current activity by fishing boats is polluting much of the Prince William Sound. Geologists have studied the effects of road deicing in the northeast and have reported that there is substantial evidence that the millions of tons of salt placed on the highways are contributing to underground water pollution. Yet the oil industry is being challenged by environmental groups that putting produced salt water back into disposal wells is contaminating and polluting the country. We need a level playing field. How can all this help a petroleum geologist? To be competitive in today`s business, we must take advantage of opportunities to learn about other sub-disciplines of our profession. Many geologists are in a survival mode, and additional education and training are necessary if we are to survive. Technical transfers from hydrocarbon extraction to environmental assessment can be undertaken if there is a desire to change. Reeducation can be achieved by an optimistic, aggressive and disciplined individual.« less

Metabolism of 1-fluoro-1,1,2-trichloroethane, 1,2-dichloro-1,1-difluoroethane, and 1,1,1-trifluoro-2-chloroethane.

PubMed

Yin, H; Jones, J P; Anders, M W

1995-03-01

1-Fluoro-1,1,2-trichloroethane (HCFC-131a), 1,2-dichloro-1,1-difluoroethane (HCFC-132b), and 1,1,1-trifluoro-2-chloroethane (HCFC-133a) were chosen as models for comparative metabolism studies on 1,1,1,2-tetrahaloethanes, which are under consideration as replacements for ozone-depleting chlorofluorocarbons (CFCs). Male Fischer 344 rats were given 10 mmol/kg ip HCFC-131a or HCFC-132b or exposed by inhalation to 1% HCFC-133a for 2 h. Urine collected in the first 24 h after exposure was analyzed by 19F NMR and GC/MS and with a fluoride-selective ion electrode for the formation of fluorine-containing metabolites. Metabolites of HCFC-131a included 2,2-dichloro-2-fluoroethyl glucuronide, 2,2-dichloro-2-fluoroethyl sulfate, dichlorofluoroacetic acid, and inorganic fluoride. Metabolites of HCFC-132b were characterized as 2-chloro-2,2-difluoroethyl glucuronide, 2-chloro-2,2-difluoroethyl sulfate, chlorodifluoroacetic acid, chlorodifluoroacetaldehyde hydrate, chlorodifluoroacetaldehyde-urea adduct, and inorganic fluoride. HCFC-133a was metabolized to 2,2,2-trifluoroethyl glucuronide, trifluoroacetic acid, trifluoroacetaldehyde hydrate, trifluoroacetaldehyde-urea adduct, inorganic fluoride, and a minor, unidentified metabolite. With HCFC-131a and HCFC-132b, glucuronide conjugates of 2,2,2-trihaloethanols were the major urinary metabolites, whereas with HCFC-133a, a trifluoroacetaldehyde-urea adduct was the major urinary metabolite. Analysis of metabolite distribution in vivo indicated that aldehydic metabolites increased as fluorine substitution increased in the order HCFC-131a < HCFC-132b < HCFC-133a. With NADPH-fortified rat liver microsomes, HCFC-133a and HCFC-132b were biotransformed to trifluoroacetaldehyde and chlorodifluoroacetaldehyde, respectively, whereas HCFC-131a was converted to dichlorofluoroacetic acid. No covalently bound metabolites were detected by 19F NMR spectroscopy.(ABSTRACT TRUNCATED AT 250 WORDS)

Recent trends in global emissions of hydrochlorofluorocarbons and hydrofluorocarbons: reflecting on the 2007 adjustments to the Montreal Protocol.

PubMed

Montzka, S A; McFarland, M; Andersen, S O; Miller, B R; Fahey, D W; Hall, B D; Hu, L; Siso, C; Elkins, J W

2015-05-14

Global-scale atmospheric measurements are used to investigate the effectiveness of recent adjustments to production and consumption controls on hydrochlorofluorocarbons (HCFCs) under the Montreal Protocol on Substances that Deplete the Ozone Layer (Montreal Protocol) and to assess recent projections of large increases in hydrofluorocarbon (HFC) production and emission. The results show that aggregate global HCFC emissions did not increase appreciably during 2007-2012 and suggest that the 2007 Adjustments to the Montreal Protocol played a role in limiting HCFC emissions well in advance of the 2013 cap on global production. HCFC emissions varied between 27 and 29 kt CFC-11-equivalent (eq)/y or 0.76 and 0.79 GtCO2-eq/y during this period. Despite slower than projected increases in aggregate HCFC emissions since 2007, total emissions of HFCs used as substitutes for HCFCs and chlorofluorocarbons (CFCs) have not increased more rapidly than rates projected [Velders, G. J. M.; Fahey, D. W.; Daniel, J. S.; McFarland, M.; Andersen, S. O. The Large Contribution of Projected HFC Emissions to Future Climate Forcing. Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 10949-10954] for 2007-2012. HFC global emission magnitudes related to this substitution totaled 0.51 (-0.03, +0.04) GtCO2-eq/y in 2012, a magnitude about two times larger than emissions reported to the United Nations Framework Convention on Climate Change (UNFCCC) for these HFCs. Assuming accurate reporting to the UNFCCC, the results imply that developing countries (non-Annex I Parties) not reporting to the UNFCCC now account for nearly 50% of global HFC emissions used as substitutes for ozone-depleting substances (ODSs). Global HFC emissions (as CO2-eq) from ODS substitution can be attributed approximately equally to mobile air conditioning, commercial refrigeration, and the sum of all other applications.

Metabolism of 1-Fluro-1,1,2-trichloroethane, 1,2-dichloro-1,1-difluoroethane, and 1,1,1-trifluoro-2-chloroethane

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

Yin, H.; Jones, J.P.; Anders, M.W.

1995-03-01

1-Fluoro-1,1,2-trichloroethane (HCFC-131a), 1,2-dichloro-1,1-difluoroethane (HCFC-132b), and 1,1,1-trifluoro-2-chloroethane (HCFC-133a) were chosen as models for comparative metabolism studies on 1,1,1,2-tetrahaloethanes, which are under consideration as replacements for ozone-depleting chlorofluorocarbons (CFCs). Male Fischer 344 rats were given 10 mmol/kg ip HCFC-131a or HCFC-132b or exposed by inhalation to 1% HCFC-133a for 2 h. Urine collected in the first 24 h after exposure was analyzed by {sup 19}F NMR and GC/MS and with a fluoride-selective ion electrode for the formation of fluorine-containing metabolites. Metabolites of HCFC-131a included 2,2-dichloro-2-fluoroethyl glucuronide, 2,2-dichloro-2-fluorethyl sulfate, dichlorofluoroacetic acid, and inorganic fluoride. Metabolites of HCFC-132b were characterized as 2-chloro-2,2-difluoroethyl glucuronide, 2-chloro-2,2-difluoroethylmore » sulfate, chlorodifluoroacetic acid, chlorodifluoroacetaldehyde hydrate, chlorodifluoroacetaldehyde-urea adduct, inorganic fluoride, and a minor, unidentified metabolite. With HCFC-131a and HCFC-132b, glucuronide conjugates of 2,2,2-trihaloethanols were the major urinary metabolites, whereas with HCFC-133a, a trifluroacetaldehyde-urea adduct was the major urinary metabolite. Analysis of metabolite distribution in vivo indicated that aldehydic metabolites increased as fluorine substitution increased in the order HCFC-131a < HCFC-132b < HCFC-133a. With NADPH-fortified rat liver microsomes, HCFC-133a and HCFC-133a and HCFC-132b were biotransformed to trifluoroacetaldehyde and chlorodifluoroacetaldehyde, respectively, whereas HCFC-131a was converted to dichlorofluoroacetic acid. No covalently bound metabolites of HCFC-131a and HCFC-133a metabolites were detected by {sup 19}F NMR spectroscopy. 18 refs., 2 figs., 3 tabs.« less

The expanding role of aerosols in systemic drug delivery, gene therapy, and vaccination.

PubMed

Laube, Beth L

2005-09-01

Aerosolized medications have been used for centuries to treat respiratory diseases. Until recently, inhalation therapy focused primarily on the treatment of asthma and chronic obstructive pulmonary disease, and the pressurized metered-dose inhaler was the delivery device of choice. However, the role of aerosol therapy is clearly expanding beyond that initial focus. This expansion has been driven by the Montreal protocol and the need to eliminate chlorofluorocarbons (CFCs) from traditional metered-dose inhalers, by the need for delivery devices and formulations that can efficiently and reproducibly target the systemic circulation for the delivery of proteins and peptides, and by developments in medicine that have made it possible to consider curing lung diseases with aerosolized gene therapy and preventing epidemics of influenza and measles with aerosolized vaccines. Each of these drivers has contributed to a decade or more of unprecedented research and innovation that has altered how we think about aerosol delivery and has expanded the role of aerosol therapy into the fields of systemic drug delivery, gene therapy, and vaccination. During this decade of innovation, we have witnessed the coming of age of dry powder inhalers, the development of new soft mist inhalers, and improved pressurized metered-dose inhaler delivery as a result of the replacement of CFC propellants with hydrofluoroalkane. The continued expansion of the role of aerosol therapy will probably depend on demonstration of the safety of this route of administration for drugs that have their targets outside the lung and are administered long term (eg, insulin aerosol), on the development of new drugs and drug carriers that can efficiently target hard-to-reach cell populations within the lungs of patients with disease (eg, patients with cystic fibrosis or lung cancer), and on the development of devices that improve aerosol delivery to infants, so that early intervention in disease processes with aerosol therapy has a high probability of success.

Dynamics and reactivity of trapped electrons on supported ice crystallites.

PubMed

Stähler, Julia; Gahl, Cornelius; Wolf, Martin

2012-01-17

The solvation dynamics and reactivity of localized excess electrons in aqueous environments have attracted great attention in many areas of physics, chemistry, and biology. This manifold attraction results from the importance of water as a solvent in nature as well as from the key role of low-energy electrons in many chemical reactions. One prominent example is the electron-induced dissociation of chlorofluorocarbons (CFCs). Low-energy electrons are also critical in the radiation chemistry that occurs in nuclear reactors. Excess electrons in an aqueous environment are localized and stabilized by the local rearrangement of the surrounding water dipoles. Such solvated or hydrated electrons are known to play an important role in systems such as biochemical reactions and atmospheric chemistry. Despite numerous studies over many years, little is known about the microscopic details of these electron-induced chemical processes, and interest in the fundamental processes involved in the reactivity of trapped electrons continues. In this Account, we present a surface science study of the dynamics and reactivity of such localized low-energy electrons at D(2)O crystallites that are supported by a Ru(001) single crystal metal surface. This approach enables us to investigate the generation and relaxation dynamics as well as dissociative electron attachment (DEA) reaction of excess electrons under well-defined conditions. They are generated by photoexcitation in the metal template and transferred to trapping sites at the vacuum interface of crystalline D(2)O islands. In these traps, the electrons are effectively decoupled from the electronic states of the metal template, leading to extraordinarily long excited state lifetimes on the order of minutes. Using these long-lived, low-energy electrons, we study the DEA to CFCl(3) that is coadsorbed at very low concentrations (∼10(12) cm(-2)). Using rate equations and direct measurement of the change of surface dipole moment, we estimated the electron surface density for DEA, yielding cross sections that are orders of magnitude higher than the electron density measured in the gas phase.

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...

Qualitative Methods in the Development of a Bilingual and Bicultural Quality of Life Outcomes Measure for Pediatric Patients With Craniofacial Conditions.

PubMed

Tapia, Viridiana Juarez; Drizin, Julia Helene; Dalle Ore, Cecilia; Nieto, Marcelo; Romero, Yajahira; Magallon, Sandra; Nayak, Rohith; Sigler, Alicia; Malcarne, Vanessa; Gosman, Amanda

2017-05-01

Craniofacial surgeons treat patients with diverse craniofacial conditions (CFCs). Yet, little is known about the health-related quality of life (HRQoL) impact of diverse CFCs. Currently, there are no suitable instruments that measure the HRQoL of patients with diverse CFCs from the perspective of children and parents. The objective of this study was to develop the items and support the content validity of a comprehensive patient and parent-reported outcomes measure. An iterative process consisting of a systematic literature review, expert opinion and in-depth interviews with patients and parents of patients with diverse CFCs was used. The literature review and expert opinion were used to generate in-depth interview questions. We interviewed 127 subjects: 80 parents of patients ages 0 to 18 years or older and 47 patients ages 7 to 18 years or older. English and Spanish speakers were represented in our sample. The majority of subjects originated from the United States and Mexico (83%). Craniofacial conditions included were cleft lip/palate, craniosynostosis, craniofacial microsomia, microtia, and dermatological conditions. Semistructured interviews were conducted until content saturation was achieved. Line-by-line analysis of interview transcripts identified HRQoL themes. Themes were interpreted and organized into larger domains that represent the conceptual framework of CFC-associated HRQoL. Themes were operationalized into items that represent the HRQoL issues of patients for both parent and patient versions. Six final bilingual and bicultural scales based on the domains derived from the literature review, expert opinion, and in-depth interviews were developed: (1) "Social Impact," (2) "Psychological Function," (3) "Physical Function," (4) "Family Impact," (5) "Appearance," And (6) "Finding Meaning." Some cultural differences were identified: in contrast to children from Mexico and other developing nations, families from the United States did not report public harassment or extremely negative public reactions to patients' CFC. Religion and spirituality were common themes in interviews of Spanish-speaking subjects but less common in interviews of English-speaking subjects. Qualitative methods involving pediatric patients with diverse CFCs and their parents in the item development process support the content validity for this bilingual and bicultural HRQoL instrument. The items developed in this study will now undergo psychometric testing in national multisite studies for validation.

The Relationship of Loss, Mean Age of Air and the Distribution of CFCs to Stratospheric Circulation and Implications for Atmospheric Lifetimes

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Stolarski, R. S.; Schoeberl, M. R.; Jackman, C. H.; Guptal, M. L.; Newman, P. A.; Nielsen, J. E.; Fleming, E. L.

2007-01-01

Man-made molecules called chlorofluorcarbons (CFCs) are broken apart in the stratosphere by high energy light, and the reactive chlorine gases that come from them cause the ozone hole. Since the ozone layer stops high energy light from reaching low altitudes, CFCs must be transported to high altitudes to be broken apart. The number of molecules per volume (the density) is much smaller at high altitudes than near the surface, and CFC molecules have a very small chance of reaching that altitude in any particular year. Many tons of CFCs were put into the atmosphere during the end of the last century, and it will take many years for all of them to be destroyed. Each CFC has an atmospheric lifetime that depends on the amount of energy required to break them apart. Two of the gases that were made the most are CFC13 and CF2C12. It takes more energy to break apart CF2C12 than CFC13, and its lifetime is about 100 years, nearly twice as long as the lifetime for CFC13. It is hard to figure out the lifetimes from surface measurements because we don't know exactly how much was released into the air each year. Atmospheric models are used to predict what will happen to ozone and other gases as the CFCs decrease and other gases like C02 continue to increase during the next century. CFC lifetimes are used to predict future concentrations and all assessment models use the predicted future concentrations. The models have different circulations and the amount of CFC lost according to the model may not match the loss that is expected according to the lifetime. In models the amount destroyed per year depends on how fast the model pushes air into the stratosphere and how much goes to high altitudes each year. This paper looks at the way the model circulation changes the lifetimes, and looks at measurements that tell us which model is more realistic. Some models do a good job reproducing the age-of-air, which tells us that these models are circulating the stratospheric air at the right speed. These same models also do a good job reproducing the amount of CFCs in the lower atmosphere where they were measured by instruments on NASA's ER-2, a research plane that flies in the lower stratosphere. The lifetime for CFC13 that is calculated using the models that do the best job matching the data is about 25% longer than most people thought. This paper shows that using these measurements to decide which models are more realistic helps us understand why their predictions are different from each other and also to decide which predictions are more likely.

Method and apparatus for vapor detection

NASA Technical Reports Server (NTRS)

Lerner, Melvin (Inventor); Hood, Lyal V. (Inventor); Rommel, Marjorie A. (Inventor); Pettitt, Bruce C. (Inventor); Erikson, Charles M. (Inventor)

1980-01-01

The method disclosed herein may be practiced by passing the vapors to be sampled along a path with halogen vapor, preferably chlorine vapor, heating the mixed vapors to halogenate those of the sampled vapors subject to halogenation, removing unreacted halogen vapor, and then sensing the vapors for organic halogenated compounds. The apparatus disclosed herein comprises means for flowing the vapors, both sample and halogen vapors, into a common path, means for heating the mixed vapors to effect the halogenation reaction, means for removing unreacted halogen vapor, and a sensing device for sensing halogenated compounds. By such a method and means, the vapors of low molecular weight hydrocarbons, ketones and alcohols, when present, such as methane, ethane, acetone, ethanol, and the like are converted, at least in part, to halogenated compounds, then the excess halogen removed or trapped, and the resultant vapors of the halogenated compounds sensed or detected. The system is highly sensitive. For example, acetone in a concentration of 30 parts per billion (volume) is readily detected.

Climate Chemistry Coupling: Ozone Loss Linked to the Unique Dynamical Structure of the Summertime Stratosphere Over the U.S. Using In Situ Aircraft, Satellite and NEXRAD Radar Observations

NASA Astrophysics Data System (ADS)

Anderson, J. G.; Wilmouth, D. M.; Smith, J. B.; Dykema, J. A.; Leroy, S. S.; Koby, T.; Clapp, C.; Bowman, K. P.

2015-12-01

A remarkable combination of meteorological and catalytic chemical factors place the summertime lower stratosphere over the U.S. in a unique position at the intersection of climate forcing and potential ozone loss in the stratosphere. The factors that conspire to establish this circumstance engages four independent considerations. First is the occurrence of severe storms in the U.S. Mid-West caused by the intersection of moist airflow from the Gulf of Mexico with airflow from higher latitudes in spring and summer. These storms are characterized by a combination of tornadoes, hail, heavy precipitation and high winds, the frequency and intensity of which are increasing with increased forcing of the climate system by the addition of CO2, CH4, N2O CFCs, and other infrared active species to the atmosphere associated with human activity. Second is the recognition that these severe storms are capable of injecting water vapor deep into the stratosphere over the U.S., with injection depths reaching the altitude of increasing inorganic halogen species formed by the photolytic breakdown of organic chorine and bromine transported into the stratosphere. Third is the recognition that the catalytic conversion of inorganic halogen species to radicals, specifically ClO and BrO, that are the rate limiting catalytic species that destroy ozone, occurs on ubiquitous sulfate-water aerosols wherever and whenever the temperature-water vapor conditions are met. These conditions are met in the Antarctic and Arctic winter vortices by virtue of temperatures below 200K at 5 ppmv water vapor, and in the summertime lower stratosphere over the U.S. by virtue of temperatures between 200 and 205K in combination with convectively injected water vapor concentrations in the range of 8 ppmv or greater. Fourth, is the recognition that the flow pattern of the lower stratosphere over the U.S. in summer is repeatedly under the control of the North American monsoon that forms an anti-cyclonic (clockwise) gyre that captures the combination of chemical species within it, retaining that chemical mix for periods up to three weeks during the months of July and August. It is within this gyre over the U.S. that the catalytic reactions can occur potentially reducing the column concentration of ozone in summer.

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 analyser, ii) sampled on sorbent tubes or iii) pressurized into Silconert2000-coated stainless steel cylinders by cryo-filling. We focus here on standards made for the gases HFC-125 and HFC-1234yf. We present here the method, the uncertainty budget as well as first results of intercomparisons to other references.

Development of an OClO Slant Column Product for the GOME-2 Sensors

NASA Astrophysics Data System (ADS)

Richter, Andreas; Wittrock, Folkard; Burrows, John P.

2016-04-01

Stratospheric ozone depletion by catalytic reactions involving halogens is one of the most prominent examples of anthropogenic impacts on the atmosphere. In spite of the rapid and successful international action to reduce emissions of CFCs and other ozone depleting substances leading to the Montreal Protocol and its amendments, ozone depletion in polar spring is still observed in both hemispheres on a regular basis. For the coming years, slow ozone recovery is expected but individual years will still see very low ozone columns depending on meteorology and possible interactions with climate change. Monitoring of both ozone and ozone depleting substances in the stratosphere remains a priority to ensure that the predicted reduction in halogen levels and recovery of ozone columns is taking place as predicted. One way to observe stratospheric chlorine activation is by measurements of OClO which can be detected by UV/visible remote sensing from the ground and from satellite. While the link between OClO levels and chlorine activation is complicated by the fact that a) OClO is not directly involved in ozone depletion but is produced by reaction of BrO and ClO and b) is rapidly photolysed at daylight, the long existing data series from both ground-based and satellite observations makes it an interesting tracer of chlorine activation. The GOME-2 instruments on the MetOp series of satellites are nadir viewing UV/vis spectrometers having the spectral coverage and resolution needed for Differential Optical Absorption Spectroscopy retrievals of OClO. With their combined lifetime of more than 15 years, they can provide a long-term data set. However, previous attempts to create an OClO product for GOME-2 suffered from large scatter in the OClO data and time-dependent offsets. Here we present an improved OClO slant column retrieval for the two instruments GOME2-A and GOME2-B. The data is shown to be of similar quality as for earlier instruments such as SCIAMACHY, and is consistent between the instruments. The time series from the two instruments nicely reproduces the large interannual variability in chlorine activation in both hemispheres. Validation with ground-based DOAS zenith-sky observations in Ny-Ålesund shows very good agreement in NH spring. Some baseline drift remains in the GOME2-A data which could be further reduced by application of an offset correction.

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.

Inhibitory activity of Paenibacillus polymyxa on the biofilm formation of Cronobacter spp. on stainless steel surfaces.

PubMed

Yang, Soonwook; Kim, Seonhwa; Ryu, Jee-Hoon; Kim, Hoikyung

2013-07-01

The objective of this study was to control the survival or biofilm formation of Cronobacter spp. on stainless steel surfaces using Paenibacillus polymyxa. The antibacterial activity of a cell-free culture supernatant (CFCS) of P. polymyxa against Cronobacter spp. was found to vary with P. polymyxa incubation time. Maximum activity occurred when P. polymyxa was incubated at 25 or 30 °C for 96 h. When the CFCS was introduced to Cronobacter spp. adhered to stainless steel strips at 25 °C for up to 72 h, the CFCS successfully inhibited Cronobacter biofilm formation. Additionally, stainless steel surfaces with a preformed P. polymyxa biofilm were exposed to Cronobacter spp. suspensions in PBS or 0.1% peptone water at 3, 5, or 7 log CFU/mL to facilitate its attachment. The Cronobacter population significantly decreased on this surface, regardless of inoculum level or carrier, when the P. polymyxa biofilm was present. However, the microbial population decreased within 6 h and remained unchanged thereafter when the surface was immersed in an inoculum suspended in 0.1% peptone water at 5 or 7 log CFU/mL. These results indicate that P. polymyxa is able to use a promising candidate competitive-exclusion microorganism to control Cronobacter spp. © 2013 Institute of Food Technologists®

Building Child Friendly Cities in the MENA region

NASA Astrophysics Data System (ADS)

Nour, Osman El Hassan M.

2013-09-01

The notion of Child Friendly Cities (CFCs) was first developed during the Second United Nations Conference on Human Settlements (HABITAT II), held in Istanbul in 1996. The concept is based on four general principles of the United Nations Convention on the rights of the child: (1) fair treatment of every child, regardless of ethnicity, gender, religion, socioeconomic background etc.; (2) top priority of the best interests of the child; (3) the child's right to a better life and development; and (4) respect of children's views. In a CFC, children are encouraged to take part in the decision making processes that affect their lives. Instead of starting yet another programme for children, the development of a CFC mobilises and connects existing agencies and actors. Giving examples of some cities in the Middle East and North Africa (MENA) region, this paper demonstrates that building CFCs has induced the development of mechanisms and structures which have enabled cities to address children's issues in a systematic manner. These mechanisms and structures include: a municipal child-friendly legal framework, local development councils and NGO networks and local municipal development offices. The author argues that in building CFCs, the role of municipal authorities is indispensable in responding to the needs of children and young people within the municipalities' mandates.

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.

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.

Determination of a wide range of volatile organic compounds in ambient air using multisorbent adsorption/thermal desorption and gas chromatography/mass spectrometry

USGS Publications Warehouse

Pankow, J.F.; Luo, W.; Isabelle, L.M.; Bender, D.A.; Baker, R.J.

1998-01-01

Adsorption/thermal desorption with multisorbent air-sampling cartridges was developed for the determination of 87 method analytes including halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. The volatilities of the compounds ranged from that of dichlorofluoromethane (CFC12) to that of 1,2,3- trichlorobenzene. The eight most volatile compounds were determined using a 1.5-L air sample and a sample cartridge containing 50 mg of Carbotrap B and 280 mg of Carboxen 1000; the remaining 79 compounds were determined using a 5-L air sample and a cartridge containing 180 mg of Carbotrap B and 70 mg of Carboxen 1000. Analysis and detection were by gas chromatography/mass spectrometry. The minimum detectable level (MDL) concentration values ranged from 0.01 parts per billion by volume (ppbv) for chlorobenzene to 0.4 ppbv for bromomethane; most of the MDL values were in the range 0.02-0.06 ppbv. No breakthrough was detected with the prescribed sample volumes. Analyte stability on the cartridges was very good. Excellent recoveries were obtained with independent check standards. Travel spike recoveries ranged from 90 to 110% for 72 of the 87 compounds. The recoveries were less than 70% for bromomethane and chloroethene and for a few compounds such as methyl acetate that are subject to losses by hydrolysis; the lowest travel spike recovery was obtained for bromomethane (62%). Blank values for all compounds were either below detection or very low. Ambient atmospheric sampling was conducted in New Jersey from April to December, 1997. Three sites characterized by low, moderate, and high densities of urbanization/traffic were sampled. The median detected concentrations of the compounds were either similar at all three sites (as with the chlorofluorocarbon compounds) or increased with the density of urbanization/traffic (as with dichloromethane, MTBE, benzene, and toluene). For toluene, the median detected concentrations were 0.23, 0.42, and 0.70 ppbv at the three sites. Analytical precision was measured using duplicate sampling. As expected, the precision deteriorated with decreasing concentration. At concentrations greater than 0.2 ppbv, most duplicates differed by less than 20%; below the MDL values, the differences between the duplicates were larger, but they were still typically less than 40%.

Groundwater residence times in Shenandoah National Park, Blue Ridge Mountains, Virginia, USA: A multi-tracer approach

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Böhlke, J.K.; Nelms, D.L.; Michel, R.L.; Schlosser, P.

2001-01-01

Chemical and isotopic properties of water discharging from springs and wells in Shenandoah National Park (SNP), near the crest of the Blue Ridge Mountains, VA, USA were monitored to obtain information on groundwater residence times. Investigated time scales included seasonal (wet season, April, 1996; dry season, August–September, 1997), monthly (March through September, 1999) and hourly (30-min interval recording of specific conductance and temperature, March, 1999 through February, 2000). Multiple environmental tracers, including tritium/helium-3 (3H/3He), chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), sulfur-35 (35S), and stable isotopes (δ18O and δ2H) of water, were used to estimate the residence times of shallow groundwater discharging from 34 springs and 15 wells. The most reliable ages of water from springs appear to be based on SF6 and 3H/3He, with most ages in the range of 0–3 years. This range is consistent with apparent ages estimated from concentrations of CFCs; however, CFC-based ages have large uncertainties owing to the post-1995 leveling-off of the CFC atmospheric growth curves. Somewhat higher apparent ages are indicated by 35S (>1.5 years) and seasonal variation of δ18O (mean residence time of 5 years) for spring discharge. The higher ages indicated by the 35S and δ18O data reflect travel times through the unsaturated zone and, in the case of 35S, possible sorption and exchange of S with soils or biomass. In springs sampled in April, 1996, apparent ages derived from the 3H/3He data (median age of 0.2 years) are lower than those obtained from SF6 (median age of 4.3 years), and in contrast to median ages from 3H/3He (0.3 years) and SF6 (0.7 years) obtained during the late summer dry season of 1997. Monthly samples from 1999 at four springs in SNP had SF6apparent ages of only 1.2 to 2.5±0.8 years, and were consistent with the 1997 SF6 data. Water from springs has low excess air (0–1 cm3 kg−1) and N2–Ar temperatures that vary seasonally. Concentrations of He and Ne in excess of solubility equilibrium indicate that the dissolved gases are not fractionated. The seasonal variations in N2–Ar temperatures suggest shallow, seasonal recharge, and the excess He and Ne data suggest waters mostly confined to gas exchange in the shallow, mountain-slope, water-table spring systems. Water from wells in the fractured rock contains up to 8 cm3 kg−1 of excess air with ages in the range of 0–25 years. Transient responses in specific conductance and temperature were observed in spring discharge within several hours of large precipitation events in September, 1999; both parameters increased initially, then decreased to values below pre-storm base-flow values. The groundwater residence times indicate that flushing rates of mobile atmospheric constituents through groundwater to streams draining the higher elevations in SNP average less than 3 years in base-flow conditions.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

PubMed

Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

2011-05-01

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (<0.1). General indices such as the BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

Functional outcomes in children and young people with dyskinetic cerebral palsy.

PubMed

Monbaliu, Elegast; De La Peña, Mary-Grace; Ortibus, Els; Molenaers, Guy; Deklerck, Jan; Feys, Hilde

2017-06-01

This cross-sectional study aimed to map the functional profile of individuals with dyskinetic cerebral palsy (CP), to determine interrelationships between the functional classification systems, and to investigate the relationship of functional abilities with dystonia and choreoathetosis severity. Fifty-five children (<15y) and young people (15-22y) (30 males, 25 females; mean age 14y 6mo, standard deviation 4y 1mo) with dyskinetic CP were assessed using the Gross Motor Function Classification System (GMFCS), Manual Ability Classification System (MACS), Communication Function Classification System (CFCS), Eating and Drinking Ability Classification System (EDACS), and Viking Speech Scale (VSS), as well as the Dyskinesia Impairment Scale. Over 50 per cent of the participants exhibited the highest limitation levels in GMFCS, MACS, and VSS. Better functional abilities were seen in EDACS and CFCS. Moderate to excellent interrelationship was found among the classification scales. All scales had significant correlation (r s =0.65 - 0.81) with dystonia severity except for CFCS in the young people group. Finally, only MACS (r s =0.40) and EDACS (r s =0.55) in the young people group demonstrated significant correlation with choreoathetosis severity. The need for inclusion of speech, eating, and drinking in the functional assessment of dyskinetic CP is highlighted. The study further supports the strategy of managing dystonia in particular at a younger age followed by choreoathetosis in a later stage. © 2017 Mac Keith Press.

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.

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 applications in biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules. PMID:23805801

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...

Method of dehalogenation using diamonds

DOEpatents

Farcasiu, Malvina; Kaufman, Phillip B.; Ladner, Edward P.; Anderson, Richard R.

2000-01-01

A method for preparing olefins and halogenated olefins is provided comprising contacting halogenated compounds with diamonds for a sufficient time and at a sufficient temperature to convert the halogenated compounds to olefins and halogenated olefins via elimination reactions.

Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites

DOEpatents

Jang, Bor Z [Centerville, OH; Zhamu, Aruna [Centerville, OH

2011-02-22

Disclosed is a method of exfoliating a layered material (e.g., graphite and graphite oxide) to produce nano-scaled platelets having a thickness smaller than 100 nm, typically smaller than 10 nm, and often between 0.34 nm and 1.02 nm. The method comprises: (a) subjecting the layered material in a powder form to a halogen vapor at a first temperature above the melting point or sublimation point of the halogen at a sufficient vapor pressure and for a duration of time sufficient to cause the halogen molecules to penetrate an interlayer space of the layered material, forming a stable halogen-intercalated compound; and (b) heating the halogen-intercalated compound at a second temperature above the boiling point of the halogen, allowing halogen atoms or molecules residing in the interlayer space to exfoliate the layered material to produce the platelets. Alternatively, rather than heating, step (a) is followed by a step of dispersing the halogen-intercalated compound in a liquid medium which is subjected to ultrasonication for exfoliating the halogen-intercalated compound to produce the platelets, which are dispersed in the liquid medium. The halogen can be readily captured and re-used, thereby significantly reducing the impact of halogen to the environment. The method can further include a step of dispersing the platelets in a polymer or monomer solution or suspension as a precursor step to nanocomposite fabrication.

Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites

DOEpatents

Jang, Bor Z [Centerville, OH; Zhamu, Aruna [Centerville, OH

2012-02-14

Disclosed is a method of exfoliating a layered material (e.g., graphite and graphite oxide) to produce nano-scaled platelets having a thickness smaller than 100 nm, typically smaller than 10 nm, and often between 0.34 nm and 1.02 nm. The method comprises: (a) subjecting the layered material in a powder form to a halogen vapor at a first temperature above the melting point or sublimation point of the halogen at a sufficient vapor pressure and for a duration of time sufficient to cause the halogen molecules to penetrate an interlayer space of the layered material, forming a stable halogen-intercalated compound; and (b) heating the halogen-intercalated compound at a second temperature above the boiling point of the halogen, allowing halogen atoms or molecules residing in the interlayer space to exfoliate the layered material to produce the platelets. Alternatively, rather than heating, step (a) is followed by a step of dispersing the halogen-intercalated compound in a liquid medium which is subjected to ultrasonication for exfoliating the halogen-intercalated compound to produce the platelets, which are dispersed in the liquid medium. The halogen can be readily captured and re-used, thereby significantly reducing the impact of halogen to the environment. The method can further include a step of dispersing the platelets in a polymer or monomer solution or suspension as a precursor step to nanocomposite fabrication.

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.

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

Pharmaceutical and Medicine Manufacturing Sector (NAICS 3254)

EPA Pesticide Factsheets

Find environmental regulatory and compliance information for the pharmaceutical manufacturing sector, including essential uses of CFCs, NESHAP for pharmaceutical production, effluent guidelines for wastewater and management of hazardous waste.

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 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.

Asthma Inhalers

MedlinePlus

... an inhaler into the lungs. But CFCs are ozone-depleting substances (ODSs) that hurt the environment. Manufacturers ... inhalers, that do not rob the atmosphere of ozone. “The FDA [Food and Drug Administration] and various ...

40 CFR 279.63 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2013 CFR

2013-07-01

...) removed from refrigeration units where the CFCs are destined for reclamation. The rebuttable presumption... than refrigeration units. (d) Record retention. Records of analyses conducted or information used to...

40 CFR 279.63 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) removed from refrigeration units where the CFCs are destined for reclamation. The rebuttable presumption... than refrigeration units. (d) Record retention. Records of analyses conducted or information used to...

40 CFR 279.63 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) removed from refrigeration units where the CFCs are destined for reclamation. The rebuttable presumption... than refrigeration units. (d) Record retention. Records of analyses conducted or information used to...

40 CFR 279.63 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2012 CFR

2012-07-01

...) removed from refrigeration units where the CFCs are destined for reclamation. The rebuttable presumption... than refrigeration units. (d) Record retention. Records of analyses conducted or information used to...

40 CFR 279.63 - Rebuttable presumption for used oil.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) removed from refrigeration units where the CFCs are destined for reclamation. The rebuttable presumption... than refrigeration units. (d) Record retention. Records of analyses conducted or information used to...

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 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.

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.

Short-lived halocarbons efficient at influencing climate through ozone loss in the upper troposphere-lower stratosphere

NASA Astrophysics Data System (ADS)

Hossaini, Ryan; Chipperfield, Martyn; Montzka, Steven; Rap, Alex; Dhomse, Sandip; Feng, Wuhu

2015-04-01

Halogenated very short-lived substances (VSLS) of both natural and anthropogenic origin are a significant source of atmospheric bromine, chlorine and iodine. Due to relatively short atmospheric lifetimes (typically <6 months), VSLS breakdown in the upper troposphere-lower stratosphere (UTLS), where ozone perturbations drive a disproportionately large climate impact compared to other altitudes. Here we present chemical transport model simulations that quantify VSLS-driven ozone loss in the UTLS and infer the climate relevance of these ozone perturbations using a radiative transfer model. Our results indicate that through their impact on UTLS ozone, VSLS are efficient at influencing climate. We calculate a whole atmosphere global mean radiative effect (RE) of -0.20 (-0.16 to -0.23) Wm-2 from natural and anthropogenic VSLS-driven ozone loss, including a tropospheric contribution of -0.12 Wm-2. In the stratosphere, the RE due to ozone loss from natural bromine-containing VSLS (e.g. CHBr3, CH2Br2) is almost half of that from long-lived anthropogenic compounds (e.g. CFCs) and normalized by equivalent chlorine is ~4 times larger. We show that the anthropogenic chlorine-containing VSLS, not regulated by the Montreal Protocol, also contribute to ozone loss in the UTLS and that the atmospheric concentration of dichloromethane (CH2Cl2), the most abundant of these, is increasing rapidly. Finally, we present evidence that VSLS have made a small yet previously unrecognized contribution to the ozone-driven radiative forcing of climate since pre-industrial times of -0.02 (-0.01 to -0.03) Wm-2. Given the climate leverage that VSLS possess, future increases to their emissions, either through continued industrial or altered natural processes, may be important for future climate forcing.

Increases in Atmospheric Chlorine from Dichloromethane, a Gas Not Controlled by the Montreal Protocol.

NASA Astrophysics Data System (ADS)

Montzka, S. A.; Hossaini, R.; Hall, B. D.; Hu, L.; Miller, B.; Siso, C.; Andrews, A. E.; Sweeney, C.; Elkins, J. W.; Chipperfield, M.

2015-12-01

Short-lived, anthropogenically produced chlorinated gases historically have not been controlled by the Montreal Protocol; their contribution to stratospheric halogen loading has been relatively small and constant. Since 2000, however, tropospheric mole fractions of dichloromethane (mean lifetime of 5 months) have increased by a factor of 2 at remote sites throughout the globe. Dichloromethane currently adds more chlorine to the atmosphere (~80 ppt) than either HCFC-141b or HCFC-142b, and the implied resulting increase in stratospheric chlorine in recent years is comparable to the increase in total Cl from HCFCs. Emissions driving this global increase have been estimated at 800 Gg/yr in 2012, which is more than half of the chlorine emitted from the three main CFCs during their peak emissions in the late 1980s. Although dichloromethane is used typically as a cleaning agent, solvent, and feedstock in the production of other chemicals, the cause of the recent atmospheric increase is not well understood. Here we will show that the substantial increase in emissions does not appear to be coming from the U.S., as our ongoing observations from tall towers and aircraft profiles over North America since 2005 show a decreasing trend in measured mole fractions in the continental boundary layer relative to the background atmosphere during this period. Instead, our data from remote sites across the Northern Hemisphere reveal a shift in the atmospheric distribution of dichloromethane since 2000 that implies increased emissions from lower latitudes in the northern hemisphere. These changing distributions will be presented and discussed, along with an exploration of the potential causes for the large inter-annual variations observed in the rate of increase and what the results suggest about the main loss mechanism for dichloromethane: oxidation by the hydroxyl radical.

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 chemistry in CMAQ and its impacts on air quality.

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).

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.

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.

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

Method of reducing chlorofluorocarbon refrigerant emissons to the atmosphere

DOEpatents

DeVault, Robert C.; Fairchild, Phillip D.; Biermann, Wendell J.

1990-01-01

A method is disclosed for reducing chloroflurocarbon (CFC) refrigerant emissions during removal or transfer or refrigerants from a vapor compression cooling system or heat pump which comprises contacting the refrigerant with a suitable sorbent material. The sorbent material allows for the storage and retention or the chlorofluorocarbon in non-gaseous form so that it does not tend to escape to the atmosphere where it would cause harm by contributing to ozone depletion. In other aspects of the invention, contacting of CFC refrigerants with sorbent material allows for purification and recycling of used refrigerant, and a device containing stored sorbent material can be employed in the detection of refrigerant leakage in a cooling system or heat pump.

Using multiple chemical indicators to assess sources of nitrate and age of groundwater in a karstic spring basin

USGS Publications Warehouse

Katz, B.; Copeland, R.; Greenhalgh, T.; Ceryak, R.; Zwanka, W.

2005-01-01

Human health and ecological concerns have arisen due to a steady increase in nitrate-N concentrations during the past 40 years in Fannin Springs (0.3-4.7 mg/L), a regional discharge point with an average flow of >2.8 m3/second (>100 ft3/second) for water from the karstic Upper Floridan aquifer (UFA). Multiple chemical indicators (major dissolved species, 15N and 18O of nitrate, dissolved gases, 78 pesticides and degradates, and 67 organic compounds typically found in domestic and industrial wastewater) and transient tracers (3H/3He, chlorofluorocarbons [CFCs], sulfur hexafluoride [SF6]) were analyzed in water samples from nine wells along three transects and in spring water to assess groundwater age and potential contaminant sources. Land use is predominantly agricultural (52 percent) and forest (31 percent) in the 320 km2 (124 mi2) spring basin, which was delineated from a potentiometric-surface map of the UFA using high-resolution water-level data. Nitrate-N concentrations were highly variable in the oxic UFA and ranged from <0.02 to 4.7 mg/L. ?? 15N-NO3 values (3.4-9.9 per mil) indicated that nitrate contamination originated from inorganic sources (synthetic fertilizer) and organic sources (manure spreading or waste disposal). Higher nitrate concentrations and the younger age of spring water relative to water from upgradient wells indicate better communication with N sources at the surface. Apparent ages of groundwater correlated positively with well depth (P < 0.05) and were younger in water from wells nearer to the spring (<8 years) compared with other wells (10-50 years). Most transient tracer concentrations were consistent with binary mixing curves representing mixtures of water recharged during the past 10 years and older water (recharged before 1940). Young water mixing fractions ranged from 0.07 to 0.90. Trace levels of herbicides found in groundwater and spring water were indicative of applications for vegetative control in agricultural and other land-use types.

An Evaluation of C1-C3 Hydrochlorofluorocarbon (HCFC) Metrics: Lifetimes, Ozone Depletion Potentials, Radiative Efficiencies, Global Warming and Global Temperature Potentials

NASA Astrophysics Data System (ADS)

Burkholder, J. B.; Papanastasiou, D. K.; Marshall, P.

2017-12-01

Hydrochlorofluorocarbons (HCFCs) have been used as chlorofluorocarbon (CFC) substitutes in a number of applications, e.g. refrigerator and air-conditioning systems. Although HCFCs have lower ozone-depletion potentials (ODPs) compared to CFCs, they are potent greenhouse gases. The twenty-eighth meeting of the parties to the Montreal Protocol on Substances that Deplete the Ozone Layer (Kigali, 2016) included a list of 274 HCFCs to be controlled under the Montreal Protocol. However, from this list, only 15 of the HCFCs have values for their atmospheric lifetime, ODP, global warming potential (GWP), and global temperature potential (GTP) that are based on fundamental experimental studies, while 48 are registered compounds. In this work, we present a comprehensive evaluation of the atmospheric lifetimes, ODPs, radiative efficiencies (REs), GWPs, and GTPs for all 274 HCFCs to be included in the Montreal Protocol. Atmospheric lifetimes were estimated based on HCFC reactivity with OH radicals and O(1D), as well as their removal by UV photolysis using structure activity relationships and reactivity trends. ODP values are based on the semi-empirical approach described in the WMO/UNEP ozone assessment. Radiative efficiencies were estimated, based on infrared spectra calculated using theoretical electronic structure methods (Gaussian 09). GWPs and GTPs were calculated relative to CO2 using our estimated atmospheric lifetimes and REs. The details of the methodology will be discussed as well as the associated uncertainties. This study has provided a consistent set of atmospheric metrics for a wide range of HCFCs that support future policy decisions. More accurate metrics for a specific HCFC, if desired, would require fundamental laboratory studies to better define the OH reactivity and infrared absorption spectrum of the compound of interest. Overall, HCFCs within the same family (isomers) show a large ODP, GWP, GTP dependence on the molecular geometry of the isomers. The atmospheric lifetime of HCFCs is predominantly determined by reaction with the OH radical, with photolysis making only a minor contribution for long-lived highly chlorinated compounds. RE values are within the 0.05 and 0.3 W m-2 ppb-1 range with highly fluorinated HCFCs having the largest RE values.

Carbon dioxide, hydrographic, and chemical data obtained during the R/Vs Roger Revelle and Thomas Thompson repeat hydrography cruises in the Pacific Ocean: CLIVAR CO 2 sections P16S-2005 (9 January - 19 February, 2005) and P16N-2006 (13 February - 30 March, 2006)

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

Kozyr, Alex; Feely, R. A.; Sabine, C. L.

2009-05-01

This report presents methods, and analytical and quality control procedures for salinity, oxygen, nutrients, total carbon dioxide (TCO 2), total alkalinity (TALK), pH, discrete CO 2 partial pressure (pCO 2), dissolved organic carbon (DOC), chlorofluorocarbons (CFCs), radiocarbon, δ13C, and underway carbon measurements performed during the P16S-2005 (9 January - 19 February 2005) and P16N-2006 (13 February - 30 March, 2006) cruises in the Pacific Ocean. The research vessel (R/V) Roger Revelle departed Papeete, Tahiti, on January 9, 2005 for the Repeat Section P16S, nominally along 150°W, ending in Wellington, New Zealand, on February 19. During this cruise, samples were takenmore » from 36 depths at 111 CTD stations between 16°S and 71°S. The Repeat Section P16N, nominally along 152°W, consisted of two legs. Leg 1 started on February 13, 2006 in Papeete, Tahiti, and finished on March 3, in Honolulu, Hawaii. The R/V Thomas G. Thompson departed Honolulu for Leg 2 on March 10, 2006 and arrived in Kodiak, Alaska, on March 30. During the P16N cruises, samples were taken from 34 or 36 depths at 84 stations between 17°S and 56.28°N. The research conducted on these cruises was part of a series of repeat hydrography sections jointly funded by the National Oceanic and Atmospheric Administration (NOAA) and the National Science Foundation (NSF) as part of the Climate Variability Program (CLIVAR)/CO 2 Repeat Hydrography Program. The P16S and P16N data sets are available free of charge as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of the oceanographic data files and this printed documentation, which describes the procedures and methods used to obtain the data.« less

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 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.

Design and verification of halogen-bonding system at the complex interface of human fertilization-related MUP PDZ5 domain with CAMK's C-terminal peptide.

PubMed

Wang, Juan; Guo, Yunjie; Zhang, Xue

2018-02-01

Calmodulin-dependent protein kinase (CAMK) is physiologically activated in fertilized human oocytes and is involved in the Ca 2+ response pathways that link the fertilization calmodulin signal to meiosis resumption and cortical granule exocytosis. The kinase has an unstructured C-terminal tail that can be recognized and bound by the PDZ5 domain of its cognate partner, the multi-PDZ domain protein (MUP). In the current study, we reported a rational biomolecular design of halogen-bonding system at the complex interface of CAMK's C-terminal peptide with MUP PDZ5 domain by using high-level computational approaches. Four organic halogens were employed as atom probes to explore the structural geometry and energetic property of designed halogen bonds in the PDZ5-peptide complex. It was found that the heavier halogen elements such as bromine Br and iodine I can confer stronger halogen bond but would cause bad atomic contacts and overlaps at the complex interface, while fluorine F cannot form effective halogen bond in the complex. In addition, the halogen substitution at different positions of peptide's aromatic ring would result in distinct effects on the halogen-bonding system. The computational findings were then verified by using fluorescence analysis; it is indicated that the halogen type and substitution position play critical role in the interaction strength of halogen bonds, and thus the PDZ5-peptide binding affinity can be improved considerably by optimizing their combination. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

Human ES cells – haematopoiesis and transplantation strategies*

PubMed Central

Kaufman, DS; Thomson, JA

2002-01-01

Human embryonic stem (ES) cells provide a novel opportunity to study early developmental events in a human system. We have used human ES cell lines, including clonally derived lines, to evaluate haematopoiesis. Co-culture of the human ES cells with irradiated bone marrow stromal cell lines in the presence of fetal bovine serum (FBS), but without other exogenous cytokines, leads to differentiation of the human ES cells within a matter of days. A portion of these differentiated cells express CD34, the best-defined marker for early haematopoietic cells. Haematopoietic colony-forming cells (CFCs) are demonstrated by methylcellulose assay. Myeloid, erythroid, megakaryocyte and multipotential CFCs can all be derived under these conditions. Enrichment of CD34+ cells derived from the human ES cells markedly increases the yield of CFCs, as would be expected for cells derived from adult bone marrow or umbilical cord blood. Transcription factors are also expressed in a manner consistent with haematopoietic differentiation. This system now presents the potential to evaluate specific conditions needed to induce or support events in early human blood development. Human ES cells are also a novel source of cells for transplantation therapies. The immunogenicity of ES cell-derived cells is unknown. The unique properties of ES cells afford the opportunity to explore novel mechanisms to prevent immune-mediated rejection. Potential strategies to overcome rejection will be presented, including creation of haematopoietic chimerism as a means to successfully transplant cells and tissues derived from human ES cells. PMID:12033728

Inhibition of quorum sensing-mediated virulence in Serratia marcescens by Bacillus subtilis R-18.

PubMed

Devi, Kannan Rama; Srinivasan, Subramaniyan; Ravi, Arumugam Veera

2018-04-13

Serratia marcescens is an opportunistic human pathogen causing various nosocomial infections, most importantly urinary tract infections (UTIs). It exhibits increased resistance towards the conventional antibiotics. This study was aimed to evaluate the anti-virulence effect of a rhizosphere soil bacterium Bacillus subtilis strain R-18 against the uropathogen S. marcescens. First, the bacterial cell-free culture supernatant (CFCS) of B. subtilis strain R-18 was evaluated for its quorum sensing inhibitory (QSI) potential against biomarker strain Chromobacterium violaceum and the test pathogen S. marcescens. The B. subtilis R-18 CFCS effectively inhibited the quorum sensing (QS)-mediated violacein pigment production in C. violaceum and prodigiosin pigment production in S. marcescens. Furthermore, B. subtilis R-18 CFCS was successively extracted with different solvent systems. Of these solvents, B. subtilis R-18 petroleum ether (PE) extract showed inhibition in biofilm formation, protease, lipase, and hemolysin productions in S. marcescens. Fourier transform infrared spectroscopic (FT-IR) analysis revealed the alterations in the cellular components of bacterial cell pellets obtained from B. subtilis R-18 PE extract treated and untreated S. marcescens. The differential gene expression study further validated the downregulation of virulence-associated genes. Characterization of the active principle in B. subtilis R-18 PE extract by gas chromatography-mass spectrometry (GC-MS) analysis showed the presence of multiple compounds with therapeutic values, which could possibly reduce the QS-dependent phenotypes in S. marcescens. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Pyrrolo isoquinolines

DOEpatents

Goodman, Mark M.; Shi, Bing Z.

2000-01-01

Compounds of the formula: ##STR1## wherein X, Y, and R, independently of one another, is each a H; halogen, wherein said halogen is selected from the group consisting of .sup.123 I, .sup.124 I, .sup.125 I, .sup.131 I, .sup.75 Br, .sup.76 Br, .sup.77 Br, .sup.82 Br, .sup.18 F, or .sup.210 At; small alkyl, small alkenyl, or small alkynyl, any of which contains from one to about six carbon atoms and optionally having a carbon atom replaced by an O or S; or halogen substituted-small alkyl, halogen substituted-small alkenyl, or halogen substituted-small alkynyl wherein said compound contains at least one radioacitve halogen. The compounds bind to the serotonin transporter. Depending upon the choice of halogen substituent, the compounds are useful for PET or SPECT imaging, diagnosis and treatment of psychiatric disorders such as depression, anxiety, obsessive-compulsive disorder, and other conditions associated with defects of serotonin transporter function.

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...

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

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.

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.

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

Estimation of transit times in a Karst Aquifer system using environmental tracers: Application on the Jeita Aquifer system-Lebanon.

NASA Astrophysics Data System (ADS)

Doummar, Joanna; Hamdan, Ahmad

2016-04-01

Estimating transit times is essential for the assessment of aquifer vulnerability to contaminants. Groundwater in karst aquifer is assumed to be relatively young due to fast preferential pathways; slow flow components are present in water stored in the fissured matrix. Furthermore, transit times are site specific as they depend on recharge rates, temperatures, elevation, and flow media; saturated and unsaturated zones. These differences create significant variation in the groundwater age in karst systems as the water sampled will be a mix of different water that has been transported through different flow pathways (fissured matrix and conduits). Several methods can be applied to estimate water transit time of an aquifer such as artificial tracers, which provide an estimate for fast flow velocities. In this study, groundwater residence times in the Jeita spring aquifer (Lebanon) were estimated using several environmental tracers such as Chlorofluorocarbons (CFCs), Sulfur Hexafluoride (SF6), Helium-Tritium (3H, 3H- 3He). Additional stable isotope and major ion analysis was performed to characterize water types. Groundwater samples were collected from six different wells in the Jeita catchment area (Jurassic Kesrouane aquifer) as well as from the spring and cave itself. The results are reproducible for the Tritium-Helium method, unlike for the CFC/SF6 methods that yielded poor results due to sampling problems. Tritium concentrations in all groundwater samples show nearly the same concentration (~2.73 TU) except for one sample with relatively lower tritium concentration (~2.26 TU). Ages ranging from 0.07 ± 0.07 years to 23.59 ± 0.00 years were obtained. The youngest age is attributed to the spring/ cave while the oldest ages were obtained in wells tapping the fissured matrix. Neon in these samples showed considerable variations and high delta Ne in some samples indicating high excess air. Four (4) samples showed extreme excess air (Delta-Ne is greater than 70 %) and the remaining 3 samples have Delta-Ne in the expected range between (10-35%). Moreover Tritium-Helium analysis has showed some radiogenic Helium (4He) in one sample along with lower tritium concentrations signifying a mixture of new groundwater with old groundwater (older than 50 yrs). Furthermore, this study is complemented with published analysis of a series of 26 artificial tracer experiments performed in the Jeita karst system (Doummar, 2012). Transit times calculated from tracer experiments ranged between 3 and 300 hours (12 days). The shortest ones were recorded in the Jeita subsurface conduit. While injections in sinkholes yielded moderate transit times, fissured matrix and unsaturated zone resulted in relatively long ones. In Lebanon this type of spatial groundwater age dating using environmental tracers was not applied to date, to the exception of grab sample analysis. A second round of sampling for Tritium-Helium, CFCs and SF6 analysis will be undertaken under different flow periods in February 2016 to validate the obtained results. References Geyer, T. 2008: Process-based characterization of flow and transport in karst aquifers at catchment scale. Dissertation, Georg-August-Universität Göttingen, 103 S. Geyer, T., and Doummar, J. 2013. Protection of the Jeita Spring: Bestimmung der mittleren Verweilzeit des Grundwassers im Einzugsgebiet der Jeita Quelle-Libanon. Special report. Protection of the Jeita Spring. Applied Geosciences. Georg August University, Göttingen.

Tropospheric observations of CFC-114 and CFC-114a with a focus on long-term trends and emissions

NASA Astrophysics Data System (ADS)

Laube, Johannes C.; Hanif, Norfazrin Mohd; Martinerie, Patricia; Gallacher, Eileen; Fraser, Paul J.; Langenfelds, Ray; Brenninkmeijer, Carl A. M.; Schwander, Jakob; Witrant, Emmanuel; Wang, Jia-Lin; Ou-Yang, Chang-Feng; Gooch, Lauren J.; Reeves, Claire E.; Sturges, William T.; Oram, David E.

2016-12-01

Chlorofluorocarbons (CFCs) are ozone-depleting substances as well as strong greenhouse gases, and the control of their production and use under the Montreal Protocol has had demonstrable benefits to both mitigation of increasing surface UV radiation and climate forcing. A global ban on consumption came into force in 2010, but there is evidence of continuing emissions of certain CFCs from a range of sources. One compound has received little attention in the literature, namely CFC-114 (C2Cl2F4). Of particular interest here is the differentiation between CFC-114 (CClF2CClF2) and its asymmetric isomeric form CFC-114a (CF3CCl2F) as atmospheric long-term measurements in the peer-reviewed literature to date have been assumed to represent the sum of both isomers with a time-invariant isomeric speciation. Here we report the first long-term measurements of the two isomeric forms separately, and find that they have different origins and trends in the atmosphere. Air samples collected at Cape Grim (41° S), Australia, during atmospheric background conditions since 1978, combined with samples collected from deep polar snow (firn) enable us to obtain a near-complete record of both gases since their initial production and release in the 1940s. Both isomers were present in the unpolluted atmosphere in comparably small amounts before 1960. The mixing ratio of CFC-114 doubled from 7.9 to 14.8 parts per trillion (ppt) between the start of the Cape Grim record in 1978 and the end of our record in 2014, while over the same time CFC-114a trebled from 0.35 to 1.03 ppt. Mixing ratios of both isomers are slowly decreasing by the end of this period. This is consistent with measurements of recent aircraft-based samples showing no significant interhemispheric mixing ratio gradient. We also find that the fraction of CFC-114a mixing ratio relative to that of CFC-114 increased from 4.2 to 6.9 % over the 37-year period. This contradicts the current tacit assumption used in international climate change and ozone depletion assessments that both isomers have been largely co-emitted and that their atmospheric concentration ratio has remained approximately constant in time. Complementary observations of air collected in Taiwan indicate a persisting source of CFC-114a in South East Asia which may have been contributing to the changing balance between the two isomers. In addition we present top-down global annual emission estimates of CFC-114 and CFC-114a derived from these measurements using a two-dimensional atmospheric chemistry-transport model. In general, the emissions for both compounds grew steadily during the 1980s, followed by a substantial reduction from the late 1980s onwards, which is consistent with the reduction of emission in response to the Montreal Protocol, and broadly consistent with bottom-up estimates derived by industry. However, we find that small but significant emissions of both isomers remain in 2014. Moreover the inferred changes to the ratio of emissions of the two isomers since the 1990s also indicate that the sources of the two gases are, in part, independent.

Estimates of residence time and related variations in quality of ground water beneath Submarine Base Bangor and vicinity, Kitsap County, Washington

USGS Publications Warehouse

Cox, S.E.

2003-01-01

Estimates of residence time of ground water beneath Submarine Base Bangor and vicinity ranged from less than 50 to 4,550 years before present, based on analysis of the environmental tracers tritium, chlorofluorocarbons (CFCs), and carbon-14 (14C), in 33 ground-water samples collected from wells tapping the ground-water system. The concentrations of multiple environmental tracers tritium, CFCs, and 14C were used to classify ground water as modern (recharged after 1953), pre-modern (recharged prior to 1953), or indeterminate. Estimates of the residence time of pre-modern ground water were based on evaluation of 14C of dissolved inorganic carbon present in ground water using geochemical mass-transfer modeling to account for the interactions of the carbon in ground water with carbon of the aquifer sediments. Ground-water samples were obtained from two extensive aquifers and from permeable interbeds within the thick confining unit separating the sampled aquifers. Estimates of ground-water residence time for all ground-water samples from the shallow aquifer were less than 45 years and were classified as modern. Estimates of the residence time of ground water in the permeable interbeds within the confining unit ranged from modern to 4,200 years and varied spatially. Near the recharge area, residence times in the permeable interbeds typically were less than 800 years, whereas near the discharge area residence times were in excess of several thousand years. In the deeper aquifers, estimates of ground-water residence times typically were several thousand years but ranged from modern to 4,550 years. These estimates of ground-water residence time based on 14C were often larger than estimates of ground-water residence time developed by particle-tracking analysis using a ground-water flow model. There were large uncertainties?on the order of 1,000-2,000 years?in the estimates based on 14C. Modern ground-water tracers found in some samples from large-capacity production wells screened in the deeper aquifer may be the result of preferential ground-water pathways or induced downward flow caused by pumping stress. Spatial variations in water quality were used to develop a conceptual model of chemical evolution of ground water. Stable isotope ratios of deuterium and oxygen-18 in the 33 ground-water samples were similar, indicating similar climatic conditions and source of precipitation recharge for all of the sampled ground water. Oxidation of organic matter and mineral dissolution increased the concentrations of dissolved inorganic carbon and common ions in downgradient ground waters. However, the largest concentrations were not found near areas of ground-water discharge, but at intermediate locations where organic carbon concentrations were greatest. Dissolved methane, derived from microbial methanogenesis, was present in some ground waters. Methanogenesis resulted in substantial alteration of the carbon isotopic composition of ground water. The NETPATH geochemical model code was used to model mass-transfers of carbon affecting the 14C estimate of ground-water residence time. Carbon sources in ground water include dispersed particulate organic matter present in the confining unit separating the two aquifers and methane present in some ground water. Carbonate minerals were not observed in the lithologic material of the ground-water system but may be present, because they have been found in the bedrock of stream drainages that contribute sediment to the study area.

Chemical Emergency Preparedness and Prevention Advisory: Hydrogen Fluoride

EPA Pesticide Factsheets

This advisory recommends ways Local Emergency Planning Committees (LEPCs) and chemical facilities can reduce risks posed by the presence of hydrogen fluoride (HF), a strong inorganic acid used to manufacture CFCs, in their communities.

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.

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.

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.

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.

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.

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.

Carbon fiber composites application in ITER plasma facing components

NASA Astrophysics Data System (ADS)

Barabash, V.; Akiba, M.; Bonal, J. P.; Federici, G.; Matera, R.; Nakamura, K.; Pacher, H. D.; Rödig, M.; Vieider, G.; Wu, C. H.

1998-10-01

Carbon Fiber Composites (CFCs) are one of the candidate armour materials for the plasma facing components of the International Thermonuclear Experimental Reactor (ITER). For the present reference design, CFC has been selected as armour for the divertor target near the plasma strike point mainly because of unique resistance to high normal and off-normal heat loads. It does not melt under disruptions and might have higher erosion lifetime in comparison with other possible armour materials. Issues related to CFC application in ITER are described in this paper. They include erosion lifetime, tritium codeposition with eroded material and possible methods for the removal of the codeposited layers, neutron irradiation effect, development of joining technologies with heat sink materials, and thermomechanical performance. The status of the development of new advanced CFCs for ITER application is also described. Finally, the remaining R&D needs are critically discussed.

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

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.

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

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

PubMed

Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena

2008-10-01

The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors are 2sigma). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 +/- 0.38 and 0.97 +/- 0.16 (errors are 2sigma) were obtained for CF(3)CF(2)CF(2)OCH(3) and CF(3)CF(2)CF(2)CH(2)OH, respectively. The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k (1) and k (2), HFE-7000 is significantly less reactive than its isomer C(3)F(7)CH(2)OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of -CF(2)- in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of -CF(2)- without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively. The studied CFCs' substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, tau (Cl) values as low as 2.5 and 0.4 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF(3)CF(2)CF(2)OCH(3), significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure-reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.

Time perspective, personality and smoking, body mass, and physical activity: an empirical study.

PubMed

Adams, Jean; Nettle, Daniel

2009-02-01

Time perspective describes how individuals conceptualize and value future events, and may be related to health behaviours. Research to date has focused on addictive behaviours, used a variety of different measures of time perspective, and not explored the role of personality. This work aimed to: explore the relationships between: five previously used measures of time perspective; time perspective and the broad domains of the five-factor model of personality; and time perspective and smoking, body mass, and physical activity after controlling for socio-demographics and personality. Cross-sectional self-report data were collected using a web based survey. Participants (N=423) were recruited via local community internet message boards in US urban areas. The survey collected information on: delay discount rate, the Consideration of Future Consequences Scale (CFCS), the future scale of the Zimbardo Time Perspective Inventory (ZTPI), subjective probability of living to age 75, and time period for financial planning, the five-factor personality inventory, smoking, body mass index (BMI), and physical activity. After controlling for socio-demographics, most markers of time perspective were significantly correlated with each other, but the strength of correlations was rarely strong. Conscientiousness, Neuroticism, Agreeableness, and Openness were associated with some markers of time perspective. After controlling for socio-demographic and personality domains, only CFCS score was associated with smoking status and BMI. There is some overlap between previously used markers of time perspective and the five-factor personality domains but this is neither strong nor consistent. Smoking and BMI, but not physical activity, are associated with CFCS, but not other measures of time perspective.

Burke-Fahn-Marsden dystonia severity, Gross Motor, Manual Ability, and Communication Function Classification scales in childhood hyperkinetic movement disorders including cerebral palsy: a 'Rosetta Stone' study.

PubMed

Elze, Markus C; Gimeno, Hortensia; Tustin, Kylee; Baker, Lesley; Lumsden, Daniel E; Hutton, Jane L; Lin, Jean-Pierre S-M

2016-02-01

Hyperkinetic movement disorders (HMDs) can be assessed using impairment-based scales or functional classifications. The Burke-Fahn-Marsden Dystonia Rating Scale-movement (BFM-M) evaluates dystonia impairment, but may not reflect functional ability. The Gross Motor Function Classification System (GMFCS), Manual Ability Classification System (MACS), and Communication Function Classification System (CFCS) are widely used in the literature on cerebral palsy to classify functional ability, but not in childhood movement disorders. We explore the concordance of these three functional scales in a large sample of paediatric HMDs and the impact of dystonia severity on these scales. Children with HMDs (n=161; median age 10y 3mo, range 2y 6mo-21y) were assessed using the BFM-M, GMFCS, MACS, and CFCS from 2007 to 2013. This cross-sectional study contrasts the information provided by these scales. All four scales were strongly associated (all Spearman's rank correlation coefficient rs >0.72, p<0.001), with worse dystonia severity implying worse function. Secondary dystonias had worse dystonia and less function than primary dystonias (p<0.001). A longer proportion of life lived with dystonia is associated with more severe dystonia (rs =0.42, p<0.001). The BFM-M is strongly linked with the GMFCS, MACS, and CFCS, irrespective of aetiology. Each scale offers interrelated but complementary information and is applicable to all aetiologies. Movement disorders including cerebral palsy can be effectively evaluated using these scales. © 2015 Mac Keith Press.

Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations.

PubMed

Visser, Ate; Schaap, Joris D; Broers, Hans Peter; Bierkens, Marc F P

2009-01-26

The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2=69%), as well as the 3H (R2=79%) and 3He (R2=76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (+/-2 sigma) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.

Endotoxin deposits on the inner surfaces of closed-face cassettes during bioaerosol sampling: a field investigation at composting facilities.

PubMed

Duquenne, Philippe; Simon, Xavier; Demange, Valérie; Harper, Martin; Wild, Pascal

2015-05-01

A set of 270 bioaerosol samples was taken from 15 composting facilities using polystyrene closed-face filter cassettes (CFCs). The objective was to measure the quantity of endotoxin deposits on the inner surfaces of the cassettes (sometimes referred to as 'wall deposits'). The results show that endotoxins are deposited on the inner surfaces of the CFCs through sampling and/or handling of samples. The quantity of endotoxins measured on inner surfaces range between 0.05 (the limit of detection of the method) and 3100 endotoxin units per cassette. The deposits can represent a large and variable percentage of the endotoxins sampled. More than a third of the samples presented a percentage of inner surface deposits >40% of the total quantity of endotoxins collected (filter + inner surfaces). Omitting these inner surface deposits in the analytical process lead to measurement errors relative to sampling all particles entering the CFC sampler, corresponding to a developing consensus on matching the inhalable particulate sampling convention. The result would be underestimated exposures and could affect the decision as to whether or not a result is acceptable in comparison to airborne concentration limits defined in terms of the inhalability convention. The results of this study suggest including the endotoxins deposited on the inner surfaces of CFCs during analysis. Further researches are necessary to investigate endotoxin deposits on the inner cassette surfaces in other working sectors. © The Author 2014. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

ORGANIC EMISSIONS FROM PILOT-SCALE INCINERATION OF CFCS

EPA Science Inventory

The paper gives results of the characterization of organic emissions resulting from the pilot-scale incineration of trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12) under varied feed concentrations. (NOTE: As a result of the Montreal Protocol, an international...

A tale of two cores: Evaluation of 210Pb dating methods of salt marsh sediments for two cores collected 30 years apart

NASA Astrophysics Data System (ADS)

Fuller, C.; Drexler, J. Z.

2016-12-01

210Pb dating of wetland sediments is commonly used to constrain recent C accumulation rates and contaminant input histories. However, uncertainties in 210Pb-derived rates and validation of accumulation and accretion rates using an independent tracer are often not reported. We describe here 210Pb and 137Cs profiles in two cores from a salt marsh in south San Francisco Bay, California, collected in 1981 and 2011 within 5 m of each other, to compare and evaluate 210Pb dating methods. In the 1981 core, unsupported 210Pb (210PbXS) was detected to 12 cm and yielded mass accumulation rates (MAR) of 0.043 and 0.036 g/cm2/y using the Constant Flux-Constant Sedimentation method (CF:CS) and Constant Rate of Supply (CRS) methods, respectively. Accretion rates (S) of 0.17 (CF:CS) and 0.12 cm/y (CRS) were calculated from these MARs. The distinct 137Cs peak at 4-6 cm in the 1981 core is in good agreement with the210Pb-based 1963 depth (3.4 and 4 cm, CF:CS and CRS, respectively). 210PbXS was detectable to 18 cm in the 2011 core, and yielded a CF:CS MAR (0.077 g/cm2/y; S = 0.35 cm/y) that is about two times greater than the mass-weighted average CRS MAR (0.044 g/cm2/y; S = 0.16 cm/y). Broad subsurface maxima in 137Cs and 239Pu were observed between 16 and 24 cm in the 2011 core, which are 5 to 11 cm deeper than the 1963 depth calculated by the 2011 and 1981 210Pb-derived MARs. The apparent migration and broadening of bomb-fallout radionuclide peaks over 30 years negates their use in validating 210Pb dating. Because of low 210PbXS activities in both cores, the base of the 210PbXS profile and integrated activity used in CRS are underestimated, resulting in the lower CRS MARs that decrease with increasing depth. The range of MARs determined for two cores within 5 m but separated by 30 years will be used as an example to evaluate the uncertainties that need to be reported with C accumulation rates and contaminant histories derived from 210Pb dating of sediment archives.

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2014 CFR

2014-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2013 CFR

2013-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2012 CFR

2012-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

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

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.

Natural and anthropogenic perturbations of the stratospheric ozone layer

NASA Technical Reports Server (NTRS)

Brasseur, Guy P.

1992-01-01

The paper reviews potential causes for reduction in the ozone abundance. The response of stratospheric ozone to solar activity is discussed. Ozone changes are simulated in relation with the potential development of a fleet of high-speed stratospheric aircraft and the release in the atmosphere of chlorofluorocarbons. The calculations are performed by a two-dimensional chemical-radiative-dynamical model. The importance of heterogeneous chemistry in polar stratospheric clouds and in the Junge layer (sulfate aerosol) is emphasized. The recently reported ozone trend over the last decade is shown to have been largely caused by the simultaneous effects of increasing concentrations of chlorofluorocarbons and heterogeneous chemistry. The possibility for a reduction in stratospheric ozone following a large volcanic eruption such as that of Mount Pinatubo in 1991 is discussed.

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.

Reversible capture and release of Cl 2 and Br 2 with a redox-active metal–organic framework

DOE PAGES

Tulchinsky, Yuri; Hendon, Christopher H.; Lomachenko, Kirill A.; ...

2017-03-28

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitantmore » release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. Finally, these results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.« less

Prediction of enthalpy and standard Gibbs energy of vaporization of haloaromatics from atomic properties.

PubMed

Monte, M J S; Almeida, A R R P; Liebman, J F

2015-11-01

Halogenated benzenes form a class of pollutants with a huge number of members - 1504 distinct benzene compounds, where one or more hydrogen atoms are replaced by halogens, may exist theoretically. This study presents a user friendly method for accurate prediction of vapor pressures and enthalpies of vaporization, at 298.15 K, of any mono or poly halobenzene compound. The derived equations for the prediction of those vaporization properties depend just on the number of each constituent halogen atom. This is a consequence of the absence of intramolecular interactions between the halogen atoms, revealed after examining vaporization results of ca. 40 halogenated benzenes. In order to rationalize the estimation equations, the contribution of the halogen atoms for the referred to above properties of vaporization was decomposed into two atomic properties - the volume and electron affinity. Extension of the applicability of the estimation method to substituted benzenes containing other substituent groups beyond halogen atoms as well as to some polycyclic aromatic species was tested with success. Copyright © 2015 Elsevier Ltd. All rights reserved.

40 CFR 63.128 - Transfer operations provisions-test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... using a scrubber or other halogen reduction device to reduce the vent stream halogen atom mass emission...)(2) shall determine the halogen atom mass emission rate prior to the combustor according to the...

40 CFR 63.128 - Transfer operations provisions-test methods and procedures.

Code of Federal Regulations, 2011 CFR

2011-07-01

... using a scrubber or other halogen reduction device to reduce the vent stream halogen atom mass emission...)(2) shall determine the halogen atom mass emission rate prior to the combustor according to the...

40 CFR 63.128 - Transfer operations provisions-test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

... using a scrubber or other halogen reduction device to reduce the vent stream halogen atom mass emission...)(2) shall determine the halogen atom mass emission rate prior to the combustor according to the...

40 CFR 63.128 - Transfer operations provisions-test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... using a scrubber or other halogen reduction device to reduce the vent stream halogen atom mass emission...)(2) shall determine the halogen atom mass emission rate prior to the combustor according to the...

40 CFR 63.128 - Transfer operations provisions-test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... using a scrubber or other halogen reduction device to reduce the vent stream halogen atom mass emission...)(2) shall determine the halogen atom mass emission rate prior to the combustor according to the...

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.

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

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.

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 averaged carbon oxidation state (OSc). The heterogeneous reaction of SOA with molecular halogens released from the simulated salt-pan at different simulated environmental conditions leads to changes of several physico-chemical features of the aerosol. However, the halogen release mechanisms are also affected by the presence of organic aerosols. One order of magnitude less BrO was detected by an active Differential Optical Absorption Spectroscopy (DOAS) instrument in the presence of SOA compared to experiments without SOA. This work was supported by the German Research Foundation within the HALOPROC project. Ofner, J., Krüger, H.-U., Grothe, H., Schmitt-Kopplin, P., Whitmore, K., and Zetzsch, C. (2011), Atmos. Chem. Phys., 11, 1-15.

Organic Halogen and Related Trace Gases in the Tropical Atmosphere: Results from Recent Airborne Campaigns Over the Pacific

NASA Astrophysics Data System (ADS)

Atlas, E. L.; Navarro, M. A.; Donets, V.; Schauffler, S.; Lueb, R.; Hendershot, R.; Gabbard, S.; Hornbrook, R. S.; Apel, E. C.; Riemer, D. D.; Pan, L.; Salawitch, R. J.; Nicely, J. M.; Montzka, S. A.; Miller, B.; Moore, F. L.; Elkins, J. W.; Hintsa, E. J.; Campos, T. L.; Quack, B.; Zhu, X.; Pope, L.

2014-12-01

Organic halogen gases, especially containing bromine and iodine, play a significant role as precursors to active halogen chemistry and ozone catalytic loss. Much of the reactive organic halogen originates from biological processes in the surface ocean, which can be quite variable by season and location. The tropics and coastal margins are potentially important sources that are being examined. The recent coordinated CONTRAST/ATTREX/CAST missions were conducted in the Western Tropical Pacific, a region that is a major transport pathway for tropospheric air entering the stratosphere. One of the goals of the missions was to identify sources, distributions, and transport of organic halogens from the ocean surface into the tropical lower stratosphere. The missions were conducted during the NH winter season, Jan-Feb, 2014. In this presentation, we will discuss the distributions and variability of organic halogen gases in the study region and will examine the input of organic halogen species into the Tropical Tropopause Layer (TTL). Comparison with other tracers, such as methyl nitrate and NMHC, will help identify source regions for these gases. We will focus on the measurements obtained in the CONTRAST and ATTREX missions with data from in-situ GC/MS measurements and whole air samples collected on the NSF GV and NASA Global Hawk aircraft. Comparisons with other recent airborne campaigns, such as HIPPO and TC4, and with several ship-based studies will provide an additional context for evaluating the variability of organic halogen species in the tropical atmosphere and their role in transporting reactive halogen compounds into the UT/LS.

Peptide selectivity between the PDZ domains of human pregnancy-related serine proteases (HtrA1, HtrA2, HtrA3, and HtrA4) can be reshaped by different halogen probes.

PubMed

Sun, Mei-Ling; Sun, Li-Mei; Wang, Yong-Qing

2018-06-01

The human HtrA family of serine proteases (HtrA1, HtrA2, HtrA3, and HtrA4) are the key enzymes associated with pregnancy and closely related to the development and progression of many pathological events. Previously, it was found that halogen substitution at the indole moiety of peptide Trp-1 residue can form a geometrically satisfactory halogen bond with the Drosophila discs large, zona occludens-1 (PDZ) domain of HtrA proteases. Here, we attempt to systematically investigate the effect of substitution with 4 halogen types and 2 indole positions on the binding affinity and specificity of peptide ligands to the 4 HtrA PDZ domains. The complex structures, interaction energies, halogen-bonding strength, and binding affinity of domain-peptide systems were modeled, analyzed, and measured via computational modeling and fluorescence-based assay. It is revealed that there is a compromise between the local rearrangement of halogen bond involving different halogen atoms and the global optimization of domain-peptide interaction; the substitution position is fundamentally important for peptide-binding affinity, while the halogen type can effectively shift peptide selectivity between the 4 domains. The HtrA1-PDZ and HtrA4-PDZ as well as HtrA2-PDZ and HtrA3-PDZ respond similarly to different halogen substitutions of peptide; -Br substitution at R2-position and -I substitution at R4-position are most effective in improving peptide selectivity for HtrA1-PDZ/HtrA4-PDZ and HtrA2-PDZ/HtrA3-PDZ, respectively; -F substitution would not address substantial effect on peptide selectivity for all the 4 domains. Consequently, the binding affinities of a native peptide ligand DSRIWWV -COOH as well as its 4 R2-halogenated counterparts were determined as 1.9, 1.4, 0.5, 0.27, and 0.92 μM, which are basically consistent with computational analysis. This study would help to rationally design selective peptide inhibitors of HtrA family members by using different halogen substitutions. Copyright © 2017 John Wiley & Sons, Ltd.

Shear bond strength of a bracket-bonding system cured with a light-emitting diode or halogen-based light-curing unit at various polymerization times

PubMed Central

Gupta, Sanjay Prasad; Shrestha, Basanta Kumar

2018-01-01

Purpose To determine and compare the shear bond strength (SBS) of bracket-bonding system cured with light-emitting diode (LED) and halogen-based light-curing unit at various polymerization times. Materials and methods Ninety six human maxillary premolar teeth extracted for orthodontic purpose were divided into four groups, according to the light-curing unit and exposure times used. In the halogen group, the specimens were light cured for 20 and 40 seconds. In the LED group, the specimens were light cured for 5 and 10 seconds. Stainless steel brackets were bonded with Enlight bonding system, stored in distilled water at 37°C for 24 hours and then submitted to SBS testing in a universal testing machine at a crosshead speed of 0.5 mm/minute. Adhesive remnant index (ARI) was used to evaluate the amount of adhesive remaining on the teeth determined by stereomicroscope at 10× magnification. Results The highest mean SBS was obtained with the halogen 40 seconds (18.27 MPa) followed by halogen 20 seconds (15.36 MPa), LED 10 seconds (14.60 MPa) and least with LED 5 seconds (12.49 MPa) group. According to analysis of variance (ANOVA) and Tukey’s multiple-comparison test, SBS of halogen 20 seconds group was not significantly different from halogen 40 seconds group, LED 5 seconds group and LED 10 seconds group, whereas halogen 40 seconds group was significantly different from LED 5 seconds and LED 10 seconds group. The method of light curing did not influence the ARI, with score 2 being predominant. Conclusion Polymerization with both halogen and LED resulted in SBS values that were clinically acceptable for orthodontic treatment in all groups. Hence, for bonding orthodontic brackets, photoactivation with halogen for 20 seconds and LED for 5 seconds is suggested. PMID:29692633

Ozone in the Atmosphere: I. The Upper Atmosphere.

ERIC Educational Resources Information Center

Phillips, Paul S.

1990-01-01

Research concerning the role of stratospheric ozone and the effect of chlorofluorocarbons on stratospheric ozone are discussed. The consequences of global ozone depletion are projected. The Montreal Protocol is reviewed. (CW)

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.

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.

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.

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 retrieve additional halogenated source gases from FTIR spectra will also be evoked. Our trend results will be critically discussed and compared with measurements performed in the northern hemisphere by the in situ networks. Acknowledgments The University of Liège contribution to the present work has primarily been supported by the AGACC-II project of the SSD program funded by the Belgian Federal Science Policy Office (BELSPO), Brussels. E. Mahieu is Research Associate with the F.R.S. - FNRS. Laboratory developments and mission expenses at the Jungfraujoch station were funded by the F.R.S. - FNRS and the Fédération Wallonie-Bruxelles, respectively. We thank the International Foundation High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG, Bern) for supporting the facilities needed to perform the observations. We further acknowledge the vital contribution from all the Belgian colleagues in performing the Jungfraujoch observations used here. References Mahieu, E., S. O'Doherty, S. Reimann, et al., First retrievals of HCFC-142b from ground-based high-resolution FTIR solar observations: application to high-altitude Jungfraujoch spectra, poster presentation at the 'EGU 2013 General Assembly', 07-12 April 2013, Vienna, Austria, 2013. [http://hdl.handle.net/2268/144709] Mahieu, E., M.P. Chipperfield, J. Notholt, et al., Recent Northern Hemisphere stratospheric HCl increase due to atmospheric circulation changes, Nature, 515, 104-107, doi:10.1038/nature13857, 2014a. Mahieu, E., R. Zander, G.C. Toon, et al., Spectrometric monitoring of atmospheric carbon tetrafluoride (CF4) above the Jungfraujoch station since 1989: evidence of continued increase but at a slowing rate, Atmos. Meas. Tech., 7, 333-344, 2014b. [http://hdl.handle.net/2268/154767] Montzka, S.A., S. Reimann, A. Engel, et al., Ozone-Depleting Substances (ODSs) and Related Chemicals, Chapter 1 in Scientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project-Report No. 52, 516 pp., World Meteorological Organization, Geneva, Switzerland, 2011. Rinsland, C.P., E. Mahieu, P. Demoulin, et al., Decrease of the Carbon Tetrachloride (CCl4) Loading above Jungfraujoch, based on High Resolution Infrared Solar Spectra recorded between 1999 and 2011, J. Quant. Spectrosc. Radiat. Transfer, 113, 1322-1329, 10.1016/j.jqsrt.2012.02.016, 2012. [http://hdl.handle.net/2268/121150] Zander, R., E. Mahieu, P. Demoulin, et al., Our changing atmosphere: Evidence based on long-term infrared solar observations at the Jungfraujoch since 1950, Sci. Total Environ., 391, 184-195, 2008. [http://hdl.handle.net/2268/2421

CHARACTERIZATION OF THE ORGANIC EMISSIONS FROM THE THERMAL DESTRUCTION OF CFCS

EPA Science Inventory

The report gives results of the characterization of organic emissions resulting from the pilot-scale incineration of trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12) under varied feed rates. (NOTE.- As a result of the Montreal Protocol, an international accord...

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.

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.

Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

PubMed

Pan, Yang; Zhang, Xiangru

2013-02-05

Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

THERMODYNAMIC PROPERTIES OF SELECTED HFC REFRIGERANTS

EPA Science Inventory

Hydrofluorocarbon (HFC) refrigerants are possible alternatives to replace ozone-depleting chlorofluorocarbon and hydrochlorofluorocarbon (HCFC) refrigerants. The flammability of a proposed new refrigerant is a major consideration in assessing its utility for a particular applicat...

Cognitive functioning in dyskinetic cerebral palsy: Its relation to motor function, communication and epilepsy.

PubMed

Ballester-Plané, Júlia; Laporta-Hoyos, Olga; Macaya, Alfons; Póo, Pilar; Meléndez-Plumed, Mar; Toro-Tamargo, Esther; Gimeno, Francisca; Narberhaus, Ana; Segarra, Dolors; Pueyo, Roser

2018-01-01

Cerebral palsy (CP) is a disorder of motor function often accompanied by cognitive impairment. There is a paucity of research focused on cognition in dyskinetic CP and on the potential effect of related factors. To describe the cognitive profile in dyskinetic CP and to assess its relationship with motor function and associated impairments. Fifty-two subjects with dyskinetic CP (28 males, mean age 24 y 10 mo, SD 13 y) and 52 typically-developing controls (age- and gender-matched) completed a comprehensive neuropsychological assessment. Gross Motor Function Classification System (GMFCS), Communication Function Classification System (CFCS) and epilepsy were recorded. Cognitive performance was compared between control and CP groups, also according different levels of GMFCS. The relationship between cognition, CFCS and epilepsy was examined through partial correlation coefficients, controlling for GMFCS. Dyskinetic CP participants performed worse than controls on all cognitive functions except for verbal memory. Milder cases (GMFCS I) only showed impairment in attention, visuoperception and visual memory. Participants with GMFCS II-III also showed impairment in language-related functions. Severe cases (GMFCS IV-V) showed impairment in intelligence and all specific cognitive functions but verbal memory. CFCS was associated with performance in receptive language functions. Epilepsy was related to performance in intelligence, visuospatial abilities, visual memory, grammar comprehension and learning. Cognitive performance in dyskinetic CP varies with the different levels of motor impairment, with more cognitive functions impaired as motor severity increases. This study also demonstrates the relationship between communication and epilepsy and cognitive functioning, even controlling for the effect of motor severity. Copyright © 2017 European Paediatric Neurology Society. Published by Elsevier Ltd. All rights reserved.

(210)Pb and compositional data of sediments from Rondonian lakes, Madeira River basin, Brazil.

PubMed

Bonotto, Daniel Marcos; Vergotti, Marcelo

2015-05-01

Gold exploration has been intensive in Brazilian Amazon over the last 40 years, where the use of mercury as an amalgam has caused abnormal Hg concentrations in water bodies. Special attention has been directed to Madeira River due to fact it is a major tributary of Amazon River and that since 1986, gold exploration has been officially permitted along a 350km sector of the river. The (21)(0)Pb method has been used to date sediments taken from nine lakes situated in Madeira River basin, Rondônia State, and to verify where anthropogenic Hg might exist due to gold exploitation in Madeira River. Activity profiles of excess (21)(0)Pb determined in the sediment cores provided a means to evaluate the sedimentation rates using a Constant Flux: Constant Sedimentation (CF:CS) and Constant Rate of Supply (CRS) of unsupported/excess (21)(0)Pb models. A significant relationship was found between the CF:CS sedimentation rates and the mean values of the CRS sedimentation rates (Pearson correlation coefficient r=0.59). Chemical data were also determined in the sediments for identifying possible relationships with Hg occurring in the area. Significant values were found in statistical correlation tests realized among the Hg, major oxides and Total Organic Carbon (TOC) content in the sediments. The TOC increased in the sediment cores accompanied by a loss on ignition (LOI) increment, whereas silica decreased following a specific surface area raising associated to the TOC increase. The CRS model always provided ages within the permitted range of the (21)(0)Pb-method in the studied lakes, whereas the CF:CS model predicted two values above 140 years. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

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...

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

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.

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.

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.

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...

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...

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.

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.

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.

Abnormal synergistic effects between Lewis acid-base interaction and halogen bond in F3B···NCX···NCM

NASA Astrophysics Data System (ADS)

Tang, Qingjie; Li, Qingzhong

2015-12-01

An abnormal synergistic effect was found between the Lewis acid-base interaction and halogen bond in triads F3B···NCX···NCM (X and M are halogen atoms), where the strong Lewis acid-base interaction between F3B and NCX has a larger enhancement than the weak halogen bond between NCX and NCM. This is in contrast with the traditional cooperative effect. It is interesting that the alkali-metal substituent as well as the heavier halogen atom play a more remarkable role in the enhancement of the interaction F3B···NCX than that of NCX···NCM, particularly, the alkali-metal substituent makes the abnormal synergistic effect be the traditional cooperative one.

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.

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.

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.

PRN 93-5: Labeling Requirements of the Clean Air Act

EPA Pesticide Factsheets

A regulation under the Clean Air Act requires a warning statement on products (including pesticide products) manufactured with or containing Class I ozone-depleting substances, including chlorofluorocarbons, methyl chloroform and carbon tetrachloride.

Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions.

PubMed

Han, Jiarui; Zhang, Xiangru; Liu, Jiaqi; Zhu, Xiaohu; Gong, Tingting

2017-08-01

Chlorine dioxide (ClO 2 ) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen (TOX), a collective parameter for all halogenated DBPs, formed in ClO 2 -treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid-liquid extraction (LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO 2 -treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE. With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols, were detected in the drinking water sample pretreated with multiple extractions; two of them, trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO 2 disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water. Copyright © 2017. Published by Elsevier B.V.

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.

Role of halogen and hydrogen bonds for stabilization of antithyroid drugs with hypohalous acids (HOX, X = I, Br, and Cl) adducts

NASA Astrophysics Data System (ADS)

El-Sheshtawy, Hamdy S.; El-Mehasseb, Ibrahim

2017-11-01

The mechanism for the inhibition of thyroid hormones by the thioamide-like antithyroid drug is a key process in the thyroid gland function. Therefore, in this study theoretical investigation of the molecular interaction between two antithyroid drugs, namely methimazol (MMI) and thiazoline-2-thione (T2T), with the hypohalous acids (HOX, X = I, Br, and Cl), which act as heme-linked halogenated species to tyrosine residue was discussed. The calculations were performed by M06-2X and MP2 using aug-cc-pVDZ level of theory. In addition, wB97xd/6-31G* level of theory was used in order to account for the dispersion forces. The results show the possible formation of three adducts, which is stabilized by halogen bond (I), both halogen and hydrogen bonds (II), two hydrogen bonds (III). The binding energies of the complexes reveals stabilization in the order III > II > I. The binding energies of the complexes was increased with increasing the electron affinity and polarizability of halogen atom, the dipole moment of the complexes (I and II), the electrostatic potential on halogen atom (Vmax:i.e σ-hole), and the charge-transfer process through the halogen bond in I. On the other hand, the binding energies of the complexes decreased with increasing the halogen atom electronegativity and the dipole moment of complex III. Natural bond orbital (NBO) analysis was used to investigate the molecular orbital interactions and the charge transfer process upon complexation.

Geomorphic Identification and Verification of Recent Sedimentation Patterns in the Woonasquatucket River, North Providence, Rhode Island

DTIC Science & Technology

2007-03-01

8 The Centre Cotton Manufacturing Company (1812).................................................................. 9...112 Data collection...sedimentation surface) derived from the CF:CS 210Pb model. Data are not available for vibracores CMS- SD-4210 and CMS-SD-4213 in 1938 and 1958 and

79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies† †Electronic supplementary information (ESI) available: 13C SSNMR spectra, powder X-ray diffractograms. See DOI: 10.1039/c8sc01094c

PubMed Central

Cerreia Vioglio, P.; Szell, P. M. J.; Chierotti, M. R.; Gobetto, R.

2018-01-01

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81Br 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 79/81Br 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 (dBr···N). Notably, 79/81Br 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 79/81Br NQR resonances. PMID:29899948

Bad Science and Its Social Implications.

ERIC Educational Resources Information Center

Zeidler, Dana L.; Sadler, Troy D.; Berson, Michael J.; Fogelman, Aimee L.

2002-01-01

Investigates three types of bad science: (1) cultural prejudice based on scientific errors (polygenism, phrenology, reification through intelligence testing); (2) unethical science (Tuskegee syphilis experiments, tobacco companies and research); and (3) unwitting errors (pesticides, chlorofluorocarbons). (Contains 50 references.) (SK)

A Synoptic View of the Ventilation and Circulation of Antarctic Bottom Water from Chlorofluorocarbons and Natural Tracers

NASA Astrophysics Data System (ADS)

Purkey, Sarah G.; Smethie, William M.; Gebbie, Geoffrey; Gordon, Arnold L.; Sonnerup, Rolf E.; Warner, Mark J.; Bullister, John L.

2018-01-01

Antarctic Bottom Water (AABW) is the coldest, densest, most prolific water mass in the global ocean. AABW forms at several distinct regions along the Antarctic coast and feeds into the bottom limb of the meridional overturning circulation, filling most of the global deep ocean. AABW has warmed, freshened, and declined in volume around the globe in recent decades, which has implications for the global heat and sea level rise budgets. Over the past three decades, the use of tracers, especially time-varying tracers such as chlorofluorocarbons, has been essential to our understanding of the formation, circulation, and variability of AABW. Here, we review three decades of temperature, salinity, and tracer data and analysis that have led to our current knowledge of AABW and how the southern component of deep-ocean ventilation is changing with time.

A Synoptic View of the Ventilation and Circulation of Antarctic Bottom Water from Chlorofluorocarbons and Natural Tracers.

PubMed

Purkey, Sarah G; Smethie, William M; Gebbie, Geoffrey; Gordon, Arnold L; Sonnerup, Rolf E; Warner, Mark J; Bullister, John L

2018-01-03

Antarctic Bottom Water (AABW) is the coldest, densest, most prolific water mass in the global ocean. AABW forms at several distinct regions along the Antarctic coast and feeds into the bottom limb of the meridional overturning circulation, filling most of the global deep ocean. AABW has warmed, freshened, and declined in volume around the globe in recent decades, which has implications for the global heat and sea level rise budgets. Over the past three decades, the use of tracers, especially time-varying tracers such as chlorofluorocarbons, has been essential to our understanding of the formation, circulation, and variability of AABW. Here, we review three decades of temperature, salinity, and tracer data and analysis that have led to our current knowledge of AABW and how the southern component of deep-ocean ventilation is changing with time.

Degree of conversion of two lingual retainer adhesives cured with different light sources.

PubMed

Usümez, Serdar; Büyükyilmaz, Tamer; Karaman, Ali Ihya; Gündüz, Beniz

2005-04-01

The aim of this study was to evaluate the degree of conversion (DC) of two lingual retainer adhesives, Transbond Lingual Retainer (TLR) and Light Cure Retainer (LCR), cured with a fast halogen light, a plasma arc light and a light-emitting diode (LED) at various curing times. A conventional halogen light served as the control. One hundred adhesive samples (five per group) were cured for 5, 10 or 15 seconds with an Optilux 501 (fast halogen light), for 3, 6 or 9 seconds with a Power Pac (plasma arc light), or for 10, 20 or 40 seconds with an Elipar Freelight (LED). Samples cured for 40 seconds with the conventional halogen lamp were used as the controls. Absorbance peaks were recorded using Fourier transform infrared (FT-IR) spectroscopy. DC values were calculated. Data were analysed using Kruskal-Wallis and Mann-Whitney U-tests. For the TLR, the highest DC values were achieved in 6 and 9 seconds with the plasma arc light. Curing with the fast halogen light for 15 seconds and with the LED for 40 seconds produced statistically similar DC values, but these were lower than those with the plasma arc light. All of these light exposures yielded a statistically significantly higher DC than 40 seconds of conventional halogen light curing. The highest DC value for the LCR was achieved in 15 seconds with the fast halogen light, then the plasma arc light curing for 6 seconds. These two combinations produced a statistically significantly higher DC when compared with the 40 seconds of conventional halogen light curing. The lowest DC for the LCR was achieved with 10 seconds of LED curing. The overall DC of the LCR was significantly higher than that of the TLR. The results suggest that a similar or higher DC than the control values could be achieved in 6-9 seconds by plasma arc curing, in 10-15 seconds by fast halogen curing or in 20 seconds by LED curing.

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 with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.

Global and regional emissions estimates of 1,1-difluoroethane (HFC-152a, CH3CHF2) from in situ and air archive observations

NASA Astrophysics Data System (ADS)

Simmonds, P. G.; Rigby, M.; Manning, A. J.; Lunt, M. F.; O'Doherty, S.; Young, D.; McCulloch, A.; Fraser, P. J.; Henne, S.; Vollmer, M. K.; Reimann, S.; Wenger, A.; Mühle, J.; Harth, C. M.; Salameh, P. K.; Arnold, T.; Weiss, R. F.; Krummel, P. B.; Steele, L. P.; Dunse, B. L.; Miller, B. R.; Lunder, C. R.; Hermansen, O.; Schmidbauer, N.; Saito, T.; Yokouchi, Y.; Park, S.; Li, S.; Yao, B.; Zhou, L. X.; Arduini, J.; Maione, M.; Wang, R. H. J.; Prinn, R. G.

2015-08-01

High frequency, ground-based, in situ measurements from eleven globally-distributed sites covering 1994-2014, combined with measurements of archived air samples dating from 1978 onward and atmospheric transport models, have been used to estimate the growth of 1,1-difluoroethane (HFC-152a, CH3CHF2) mole fractions in the atmosphere and the global emissions required to derive the observed growth. HFC-152a is a significant greenhouse gas but since it does not contain chlorine or bromine, HFC-152a makes no direct contribution to the destruction of stratospheric ozone and is therefore used as a substitute for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). HFC-152a has exhibited substantial atmospheric growth since the first measurements reaching a maximum annualised global growth rate of 0.81 ± 0.05 ppt yr-1 in 2006, implying a substantial increase in emissions up to 2006. However, since 2007, the annualised rate of growth has slowed to 0.38 ± 0.04 ppt yr-1 in 2010 with a further decline to an average rate of change in 2013-2014 of -0.06 ± 0.05 ppt yr-1. The average Northern Hemisphere (NH) mixing ratio in 1994 was 1.2 ppt rising to a mixing ratio of 10.2 ppt in December 2014. Average annual mixing ratios in the Southern Hemisphere (SH) in 1994 and 2014 were 0.34 and 4.4 ppt, respectively. We estimate global emissions of HFC-152a have risen from 7.3 ± 5.6 Gg yr-1 in 1994 to a maximum of 54.4 ± 17.1 Gg yr-1 in 2011, declining to 52.5 ± 20.1 Gg yr-1 in 2014 or 7.2 ± 2.8 Tg-CO2 eq yr-1. Analysis of mixing ratio enhancements above regional background atmospheric levels suggests substantial emissions from North America, Asia and Europe. Global HFC emissions (so called "bottom up" emissions) reported by the United Nations Framework Convention on Climate Change (UNFCCC) are based on cumulative national emission data reported to the UNFCCC, which in turn are based on national consumption data. There appears to be a significant underestimate of "bottom-up" global emissions of HFC-152a, possibly arising from largely underestimated USA emissions and undeclared Asian emissions.

Delivery of fenoterol via Respimat, a novel 'soft mist' inhaler. a randomised, double-blind (within device), placebo-controlled, cross-over, dose-ranging study in asthmatic patients.

PubMed

van Noord, J A; Smeets, J J; Creemers, J P; Greefhorst, L P; Dewberry, H; Cornelissen, P J

2000-01-01

The phase-out of chlorofluorocarbons (CFCs) for metered dose inhalers (MDIs) has prompted the development of alternative propellants and the design of propellant-free devices for inhalation therapy. This study was carried out to determine the dose of fenoterol inhaled from Respimat (RMT), a new propellant-free soft mist inhaler, which is equivalent in terms of efficacy and safety to 1 puff of either 100 or 200 microg fenoterol inhaled from a conventional CFC-MDI (Berotec). Sixty-two asthmatic patients (35 male, 27 female) with a mean baseline FEV(1) of 1.7 liters, corresponding to 55% of the predicted normal value, were randomized at two study centers to 4 of a total of 8 possible treatments: placebo; 12.5, 25, 50, 100, or 200 microg fenoterol via RMT, and 100 or 200 microg fenoterol delivered via the MDI. Fifty-nine patients completed the study as planned. Results of the therapeutic equivalence test for the primary endpoint, average FEV(1) (AUC(0-6))/6 and for the secondary endpoint, peak FEV(1), showed that the 12.5- and 25-microg fenoterol doses administered via RMT were equivalent to the 100 microg fenoterol dose from the MDI. The 50-, 100- and 200-microg fenoterol doses delivered by RMT did not meet the criterion for therapeutic equivalence with the 100-microg dose from the MDI, and if tested for a difference would have been significantly different in favor of RMT. All 5 RMT fenoterol doses were therapeutically equivalent to the MDI 200-microg fenoterol dose. Headache, reported by 4 patients on test days and 2 patients between test days in those randomized to RMT, was the most common adverse event, but the active treatments were generally well tolerated with no dose-dependent increases in incidence or severity of adverse events observed. The results from the study suggest that safe and efficacious bronchodilation can be obtained from single-dose fenoterol administered via RMT. Use of lower absolute doses to obtain a clinically significant improvement in pulmonary function may be possible because of the increased lung deposition achievable with the novel soft mist inhaler. Copyright 2000 S. Karger AG, Basel

O(1D) kinetic study of key ozone depleting substances and greenhouse gases.

PubMed

Baasandorj, Munkhbayar; Fleming, Eric L; Jackman, Charles H; Burkholder, James B

2013-03-28

A key stratospheric loss process for ozone depleting substances (ODSs) and greenhouse gases (GHGs) is reaction with the O((1)D) atom. In this study, rate coefficients, k, for the O((1)D) atom reaction were measured for the following key halocarbons: chlorofluorocarbons (CFCs) CFCl3 (CFC-11), CF2Cl2 (CFC-12), CFCl2CF2Cl (CFC-113), CF2ClCF2Cl (CFC-114), CF3CF2Cl (CFC-115); hydrochlorofluorocarbons (HCFCs) CHF2Cl (HCFC-22), CH3CClF2 (HCFC-142b); and hydrofluorocarbons (HFCs) CHF3 (HFC-23), CHF2CF3 (HFC-125), CH3CF3 (HFC-143a), and CF3CHFCF3 (HFC-227ea). Total rate coefficients, kT, corresponding to the loss of the O((1)D) atom, were measured over the temperature range 217-373 K using a competitive reactive technique. kT values for the CFC and HCFC reactions were >1 × 10(-10) cm(3) molecule(-1) s(-1), except for CFC-115, and the rate coefficients for the HFCs were in the range (0.095-0.72) × 10(-10) cm(3) molecule(-1) s(-1). Rate coefficients for the CFC-12, CFC-114, CFC-115, HFC-23, HFC-125, HFC-143a, and HFC-227ea reactions were observed to have a weak negative temperature dependence, E/R ≈ -25 K. Reactive rate coefficients, kR, corresponding to the loss of the halocarbon, were measured for CFC-11, CFC-115, HCFC-22, HCFC-142b, HFC-23, HFC-125, HFC-143a, and HFC-227ea using a relative rate technique. The reactive branching ratio obtained was dependent on the composition of the halocarbon and the trend in O((1)D) reactivity with the extent of hydrogen and chlorine substitution is discussed. The present results are critically compared with previously reported kinetic data and the discrepancies are discussed. 2D atmospheric model calculations were used to evaluate the local and global annually averaged atmospheric lifetimes of the halocarbons and the contribution of O((1)D) chemistry to their atmospheric loss. The O((1)D) reaction was found to be a major global loss process for CFC-114 and CFC-115 and a secondary global loss process for the other molecules included in this study.

A 17-year record of environmental tracers in spring discharge, Shenandoah National Park, Virginia, USA: use of climatic data and environmental conditions to interpret discharge, dissolved solutes, and tracer concentrations

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

2014-01-01

A 17-year record (1995–2012) of a suite of environmental tracer concentrations in discharge from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park (SNP), Virginia, USA, reveals patterns and trends that can be related to climatic and environmental conditions. These data include a 12-year time series of monthly sampling at five springs, with measurements of temperature, specific conductance, pH, and discharge recorded at 30-min intervals. The monthly measurements include age tracers (CFC-11, CFC-12, CFC-113, CFC-13, SF6, and SF5CF3), dissolved gases (N2, O2, Ar, CO2, and CH4), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF6) concentrations (in pptv) in spring discharge closely follow the concurrent monthly measurements of their atmospheric mixing ratios measured at the Air Monitoring Station at Big Meadows, SNP, indicating waters 0–3 years in age. A 2-year (2001–2003) record of unsaturated zone air displayed seasonal deviations from North American Air of ±10 % for CFC-11 and CFC-113, with excess CFC-11 and CFC-113 in peak summer and depletion in peak winter. The pattern in unsaturated zone soil CFCs is a function of gas solubility in soil water and seasonal unsaturated zone temperatures. Using the increase in the SF6 atmospheric mixing ratio, the apparent (piston flow) SF6 age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF6 concentration and concentrations of dissolved solutes (SiO2, Ca2+, Mg2+, Na+, Cl−, and HCO3−) in spring discharge demonstrate a fraction of recent recharge following large precipitation events. The output of solutes in the discharge of springs minus the input from atmospheric deposition per hectare of watershed area (mol ha−1 a−1) were approximately twofold greater in watersheds draining the regolith of Catoctin metabasalts than that of granitic gneisses and granitoid crystalline rocks. The stable isotopic composition of water in spring discharge broadly correlates with the Oceanic Niño Index. Below normal precipitation and enriched stable isotopic composition were observed during El Niño years.

Isotope Geochemistry and Chronology of Offshore Ground Water Beneath Indian River Bay, Delaware

USGS Publications Warehouse

Böhlke, John Karl; Krantz, David E.

2003-01-01

Results of geophysical surveys in Indian River Bay, Delaware, indicate a complex pattern of salinity variation in subestuarine ground water. Fresh ground-water plumes up to about 20 meters thick extending hundreds of meters offshore are interspersed with saline ground water, with varying degrees of mixing along the salinity boundaries. It is possible that these features represent pathways for nutrient transport and interaction with estuarine surface water, but the geophysical data do not indicate rates of movement or nutrient sources and reactions. In the current study, samples of subestuarine ground water from temporary wells with short screens placed 3 to 22 meters below the sediment-water interface were analyzed chemically and isotopically to determine the origins, ages, transport pathways, and nutrient contents of the fresh and saline components. Apparent ground-water ages determined from chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and helium isotopes (3He and 4He) commonly were discordant, but nevertheless indicate that both fresh and saline ground waters ranged from a few years to at least 50 years in age. Tritium-helium (3H-3He) ages, tentatively judged to be most reliable, indicate that stratified offshore freshwater plumes originating in distant recharge areas on land were bounded by relatively young saline water that was recharged locally from the overlying estuary. Undenitrified and partially denitrified nitrate of agricultural or mixed origin was transported laterally beneath the estuary in oxic and suboxic fresh ground water. Ammonium produced by anaerobic degradation of organic matter in estuarine sediments was transported downward in suboxic saline ground water around the freshwater plumes. Many of the chemical and isotopic characteristics of the subestuarine ground waters are consistent with conservative mixing of the fresh (terrestrial) and saline (estuarine) endmember water types. These data indicate that freshwater plumes detected by geophysical surveys beneath Indian River Bay represent lateral continuations of the active surficial nitrate-contaminated freshwater flow systems originating on land, but they do not indicate directly the magnitude of fresh ground-water discharge or nutrient exchange with the estuary. There is evidence that some of the terrestrial ground-water nitrate is reduced before discharging directly beneath the estuary. Local estuarine sediment-derived ammonium in saline pore water may be a substantial benthic source of nitrogen in offshore areas of the estuary.

C-I···π Halogen Bonding Driven Supramolecular Helix of Bilateral N-Amidothioureas Bearing β-Turns.

PubMed

Cao, Jinlian; Yan, Xiaosheng; He, Wenbin; Li, Xiaorui; Li, Zhao; Mo, Yirong; Liu, Maili; Jiang, Yun-Bao

2017-05-17

We report the first example of C-I···π halogen bonding driven supramolecular helix in highly dilute solution of micromolar concentration, using alanine based bilateral I-substituted N-amidothioureas that contain helical fragments, the β-turn structures. The halogen bonding interactions afford head-to-tail linkages that help to propagate the helicity of the helical fragments. In support of this action of the halogen bonding, chiral amplification was observed in the supramolecular helix formed in acetonitrile solution. The present finding provides alternative tools in the design of self-assembling macromolecules.

Aromatic fluorine compounds. XI. Replacement of chlorine by fluorine in halopyridines

USGS Publications Warehouse

Finger, G.C.; Starr, L.D.; Dickerson, D.R.; Gutowsky, H.S.; Hamer, J.

1963-01-01

The ??-halogenated pyridines react with potassium fluoride in various solvents to give replacement of the ??-halogen by fluorine. A 50% yield of 2-fluoropyridine was obtained from 2-chloropyridine by heating with potassium fluoride in dimethyl sulfone or tetramethylene sulfone for twenty-one days; 2-bromopyridine gave a similar yield with a heating period of only seven days. The ??-halogens of the polyhalopyridines undergo the exchange reaction more readily than do the halogens of the ??-monohalopyridines. The proposed structures of the fluoropyridines are supported by alternate syntheses and by n.m.r. studies.

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

Richey, D.G.; Driscoll, C.T.; Likens, G.B.

Treesearch

1997-01-01

The phase out of chlorofluorocharbons (CFCs) has resulted in the use of hydrochlorofluorocharbons (HCFCs) and hydrofluorocarbons (HFCs) as environmentally acceptable alternative chemicles. Trifluoroacetic acid (TFA) has been identified as a degradation byproduct of these compounds, which largely returns the Earth's surface via precipitation. Little is known about...

The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles

EPA Science Inventory

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens...

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.

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.

Probability of Unmixed Young Groundwater (defined using chlorofluorocarbon-11 concentrations and tritium activities) in the Eagle River Watershed Valley-Fill Aquifer, Eagle County, North-Central Colorado, 2006-2007

USGS Publications Warehouse

Rupert, Michael G.; Plummer, Niel

2009-01-01

This raster data set delineates the predicted probability of unmixed young groundwater (defined using chlorofluorocarbon-11 concentrations and tritium activities) in groundwater in the Eagle River watershed valley-fill aquifer, Eagle County, North-Central Colorado, 2006-2007. This data set was developed by a cooperative project between the U.S. Geological Survey, Eagle County, the Eagle River Water and Sanitation District, the Town of Eagle, the Town of Gypsum, and the Upper Eagle Regional Water Authority. This project was designed to evaluate potential land-development effects on groundwater and surface-water resources so that informed land-use and water management decisions can be made. This groundwater probability map and its associated probability maps were developed as follows: (1) A point data set of wells with groundwater quality and groundwater age data was overlaid with thematic layers of anthropogenic (related to human activities) and hydrogeologic data by using a geographic information system to assign each well values for depth to groundwater, distance to major streams and canals, distance to gypsum beds, precipitation, soils, and well depth. These data then were downloaded to a statistical software package for analysis by logistic regression. (2) Statistical models predicting the probability of elevated nitrate concentrations, the probability of unmixed young water (using chlorofluorocarbon-11 concentrations and tritium activities), and the probability of elevated volatile organic compound concentrations were developed using logistic regression techniques. (3) The statistical models were entered into a GIS and the probability map was constructed.

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-MORB from Macquarie Island [Kendrick et al., 2012]. The concentrations are not related to superficial processes. The on-axis samples display a relatively restricted range (6.9-8.6wt%) of MgO contents, suggesting no control of the crystallisation processes. The basalts were erupted between 3900-2000 m bsl, so no appreciable degassing of halogens would be expected. The strong correlation, which exists between the halogens and other incompatible elements (e.g., Rb, La), also rules out seawater assimilation. Therefore, concentrations and elemental ratios can be directly linked to melting and source features. Estimates of halogens abundances in the depleted-mantle source are 4 ppm Cl, 14 ppb Br and 0.3 ppb I. These low abundances, which are in agreement with values derived for sub-continental mantle from coated diamonds [Burgess et al., 2002], suggest that, like noble gases, the upper mantle is degassed of its halogens. Critically, the halogen elemental ratios show no significant variations along the axial ridge and off-axis ridge or between N-MORB and E-MORB: Br/Cl=0.00147±0.00014, I/Cl=0.000021±0.000005; I/Br=0.0142±0.0036. These ratios are similar to E-MORB from Macquarie Island [Kendrick et al., 2012]. This observation is thus not consistent with subduction as a source of halogen enrichment in E-MORB.

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 several other halogenated VOCs.

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

PubMed

Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

2018-02-20

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

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.

IDENTIFICATION OF CFC AND HCFC SUBSTITUTES FOR BLOWING POLYURETHANE FOAM INSULATION PRODUCTS

EPA Science Inventory

The report gives results of a cooperative effort to identiry chlorofluorocarbons and hydrochlorofluorocarbon substitutes for blowing polyurethane foam insulation products. The substantial ongoing effort is identifying third-generation blowing agets for polyurethane foams to repla...

Projects for a Healthy Planet: Simple Environmental Experiments for Kids.

ERIC Educational Resources Information Center

Levine, Shar; Grafton, Allison

1992-01-01

Presents two experiments about ozone related topics. The first experiment examines the effect of sunlight on newsprint and relates this to human skin. The second demonstrates how chemicals, and specifically chlorofluorocarbons travel through the air. (MCO)

Global Warming: How Much and Why?

ERIC Educational Resources Information Center

Lanouette, William

1990-01-01

Summarizes the history of the study of global warming and includes a discussion of the role of gases, like carbon dioxide, methane, and chlorofluorocarbon (CFC). Discusses modern research on the global warming, including computer modelling and the super-greenhouse effect. (YP)

MOBILE AIR-CONDITIONING RECYCLING MANUAL

EPA Science Inventory

The report gives guidelines on the recovery and recycle of the chlorofluorocarbon (CFC), dichlorodifluoromethane (CFC-12), from mobile air conditions. It is intended for wide distribution internationally and is especially for use by developing countries and the World Bank to ass...

EVALUATION OF REFRIGERANT FROM MOBILE AIR CONDITIONERS

EPA Science Inventory

The report gives results of a project to provide a scientific basis for choosing a reasonable standard of purity for recycled chlorofluorocarbon (CFC) refrigerant in operating automobile air conditioners. The quality of refrigerant from air conditioners in automobiles of differen...

AEROSOL INDUSTRY SUCCESS IN REDUCING CFC PROPELLANT USAGE

EPA Science Inventory

Part I of this report discusses the U.S. aerosol industry's experience in converting from chlorofluorocarbon (CFC) propellants to alternative aerosol formulations. Detailed examples of non-CFC formulations are provided for 28 categories of aerosol products. ydrocarbon propellants...

EXPERIMENTAL INVESTIGATION OF PIC FORMATION IN CFC INCINERATION

EPA Science Inventory

The report gives results of the collection of combustion emission characterization data from chlorofluorocarbon (CFC) incineration. A bench scale test program to provide emission characterization data from CFC incineration was developed and performed, with emphasis on the format...

Emissions of Bromine and Iodine from the Marine Environment in New Zealand

NASA Astrophysics Data System (ADS)

Martinez-Aviles, M.; Kreher, K.; Johnston, P. V.; Hay, T.; Thomas, A.; Schofield, R.

2009-12-01

As noted in the WMO/UNEP Scientific Assessment of Ozone Depletion: 2006, halogenated very short-lived substances (VSLS) contribute to the atmospheric budget of halogens and thereby lead to substantial decreases in ozone and increases in surface UV radiation in the tropics and mid-latitudes. Halogenated VSLS are primarily of natural origin; oceanic emissions constitute the largest source providing 90-95% of the total global flux to the atmosphere. Macro algae in the ocean appear to be an important source of polyhalogenated VSLS. Oxidation of halogenated VSLS in the atmosphere (i.e. photolysis and reactions with OH) produces halogen oxide radicals (e.g. ClO, BrO, IO) which have been suggested as the main component of gas-phase halogens. Countries with long coastlines and little land suitable for forestation are investigating the possibility of industrial scale marine kelp farming as a means of carbon sequestration. This marine analogy of the Kyoto Protocol forest has been thought as a means to contribute to climate change mitigation. Knowledge of how natural emissions of VSLS will respond to both the drivers of climate change (e.g. changes in CO2 and land use) and to the consequences of climate change (e.g. changes in sea surface temperature and wind stress) is very limited. As a result, it is imperative that observational studies are performed to quantify the contributions of these natural VSLS to halogen loading in the troposphere and, subsequently, in the stratosphere. For this, transport and degradation processes of the source gases and product gases need to be studied and quantified. A key question surfacing from the WMO Assessment is to what extent halogenated VSLS contribute to atmospheric Bry and Iy. During a field campaign conducted during the spring of 2009, measurements of BrO and IO were made along the coastline of the South Island of New Zealand using a portable Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) spectrometer with the aim of determining coastal sites where high active halogen release could be observed. The selected sites had high biomass concentration of marine algae that would be exposed by low tides. Local macro algae type, tidal height, sunlight, temperature, and wind speed were recorded and correlated to the resulting data in order to better understand the environmental factors that modulate the emissions of halogen oxides from the marine environment to the troposphere. Results of this multi-disciplinary approach to studying brominated VSLS and their atmospheric implications are presented. As well, the chemical processes taking place and producing these halogen oxides are discussed in a thorough manner. This study contributes to a better understanding of the origin of bromine and iodine in the lowermost atmosphere (i.e. marine boundary layer). Particularly, the role that natural emissions of halogenated VSLS from the ocean may play in the halogen budget of the lower atmosphere is addressed by quantitatively understanding key links in this chain so that its potential future impacts on atmospheric chemistry, surface UV radiation, and the biosphere can be thoroughly assessed.

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.

Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

PubMed

Lim, Seung Joo; Fox, Peter

2014-02-01

The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

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

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 carbonaceous chondrites should be considered when we assess Earth's halogen abundance relative to CI. [1] Lodders (2003) Astr J 591:1220-47. [2] Sharp et al. (2013) EPSL 369/70: 71-7. [3] Dreibus et al. (1979) Phys Chem Earth 11:33-8. [4] Goles et al. (1967) GCA 31: 1771-7. [5] Reed and Allen (1966) GCA 30: 779-800. [6] Greenland & Lovering (1965) GCA 29: 821-58.

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

Halogen Chemistry at North American Coastal Sites

NASA Astrophysics Data System (ADS)

Stutz, J.; Pikelnaya, O.; Laskin, A.; Sumner, A.; Jobson, B. T.; Finley, B.; Lawler, M.; Saltzman, E. S.; Pszenny, A. A.; Deegan, B.

2007-12-01

In recent years observational evidence has emerged that reactive halogen species (RHS), such as chlorine atoms, and bromine and iodine oxides, are present in coastal areas. Their chemistry can be significant as they catalytically destroy O3; oxidize hydrocarbons, dimethylsulfide, and S(IV); and modify NOx and HOx cycling. Despite their potential importance our observational database on RHS is still very limited. Most observations of RHS thus far have been made in clean areas and very few observations along the North American coast have been made. Here we will review our current understanding of RHS chemistry in both clean and polluted environments. Recent observations at coastal areas around the world will be discussed. We will also give an overview of an experiment performed by our group in Malibu, CA in October 2006 and present initial results. A suite of trace gases and environmental parameters, including halogen molecules, halogen oxides, Cl + VOC reaction products, aerosol composition, O3, NOx, CO, VOCs, meteorology, and radiation, were measured during a three week period. In addition, Cl + VOC reaction products were measured at two locations in urban Los Angeles. Clear evidence for the presence of various halogen species on the California coast was found. Observations during periods with relatively clean marine air and during times where our site was in the outflow of Los Angeles show the impact of pollution on coastal atmospheric chemistry. Our observations will be compared to earlier studies of halogen chemistry at coastal areas to further advance our understanding of halogen chemistry.

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.

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.

INVESTIGATION OF POSSIBLE USES OF CFC/HALON CHEMICALS

EPA Science Inventory

The report documents an investigation of the possibility of alternate uses for surplus chlorofluorocarbon (CFC)/halon chemicals as they are replaced in their traditional service roles. hese uses may be beneficial new products or substances that are nonhazardous to the environment...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2011 CFR

2011-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... Compliance Requirements § 63.2465 What requirements must I meet for process vents that emit hydrogen halide... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

Building Child Friendly Cities in the MENA Region

ERIC Educational Resources Information Center

Nour, Osman El Hassan N.

2013-01-01

The notion of Child Friendly Cities (CFCs) was first developed during the Second United Nations Conference on Human Settlements (HABITAT II), held in Istanbul in 1996. The concept is based on four general principles of the United Nations "Convention on the rights of the child": (1) fair treatment of every child, regardless of ethnicity,…

Potentially probiotic Lactobacillus strains from traditional Kurdish cheese.

PubMed

Hashemi, Seyed Mohammad Bagher; Shahidi, Fakhri; Mortazavi, Seyed Ali; Milani, Elnaz; Eshaghi, Zarrin

2014-03-01

In this study, the probiotic potential of Lactobacillus strains isolated from traditional Kurdish cheese was investigated. The Lactobacillus strains were examined for resistance to gastric acidity and bile toxicity, antimicrobial activities, autoaggregation, coaggregation, hydrophobicity, adhesion to Caco-2 cells, and antibiotic susceptibility. The results showed that all strains tested tolerate acid gastric conditions (pH 2.0 and 3.0), and all of them were bile resistant (at 0.3 and 1% concentration). Although no antibacterial activity was detected in vitro assay for the treated (neutralized to pH 6.5 and treated with catalase) cell-free culture supernatant (CFCS) of strains, untreated CFCS showed strong antagonistic activity against two known pathogens bacteria. All strains exhibited a strong autoaggregating phenotype and manifested a high degree of coaggregation with pathogens. On the other hand, majority of studied strains were found sensitive to different antibiotics, such as ampicillin, penicillin, ciprofloxacin, chloramphenicol, erythromycin, rifampicin, and tetracycline, and were resistant to vancomycin and streptomycin. Finally, isolated strains showed good hydrophobicity and adherence to Caco-2 cell line, so they could be exploited for food manufacture.

Nontypical iodine–halogen bonds in the crystal structure of (3 E )-8-chloro-3-iodomethylidene-2,3-dihydro-1,4-oxazino[2,3,4- ij ]quinolin-4-ium triiodide

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

Bartashevich, E. V.; Batalov, V. I.; Yushina, I. D.

2016-03-23

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C 12H 8ClINO +·I 3 -, described by X-ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. The influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.

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.

Photochemically and Thermally Driven Full-Color Reflection in a Self-Organized Helical Superstructure Enabled by a Halogen-Bonded Chiral Molecular Switch.

PubMed

Wang, Hao; Bisoyi, Hari Krishna; Wang, Ling; Urbas, Augustine M; Bunning, Timothy J; Li, Quan

2018-02-05

Supramolecular approaches toward the fabrication of functional materials and systems have been an enabling endeavor. Recently, halogen bonding has been harnessed as a promising supramolecular tool. Herein we report the synthesis and characterization of a novel halogen-bonded light-driven axially chiral molecular switch. The photoactive halogen-bonded chiral switch is able to induce a self-organized, tunable helical superstructure, that is, cholesteric liquid crystal (CLC), when doped into an achiral liquid crystal (LC) host. The halogen-bonded switch as a chiral dopant has a high helical twisting power (HTP) and shows a large change of its HTP upon photoisomerization. This light-driven dynamic modulation enables reversible selective reflection color tuning across the entire visible spectrum. The chiral switch also displays a temperature-dependent HTP change that enables thermally driven red, green, and blue (RGB) reflection colors in the self-organized helical superstructure. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Two-dimensional networks of brominated Y-shaped molecules on Au(111)

NASA Astrophysics Data System (ADS)

Jeon, Un Seung; Chang, Min Hui; Jang, Won-Jun; Lee, Soon-Hyung; Han, Seungwu; Kahng, Se-Jong

2018-02-01

In the design of supramolecular structures, Y-shaped molecules are useful to expand the structures in three different directions. The supramolecular structures of Y-shaped molecules with three halogen-ligands on surfaces have been extensively studied, but much less are done for those with six halogen-ligands. Here, we report on the intermolecular interactions of a Y-shaped molecule, 1,3,5-Tris(3,5-dibromophenyl)benzene, with six Br-ligands studied using scanning tunneling microscopy (STM). Honeycomb-like structures were observed on Au(111), and could be explained with chiral triple-nodes made of three Br···Br halogen bonds. Molecular models were proposed based on STM images and reproduced with density-functional theory calculations. Although the molecule has six Br-ligands, only three of them form Br···Br halogen bonds because of geometrical restrictions. Our study shows that halogenated Y-shaped molecules will be useful components for building supramolecular structures.

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.

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.

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.

Economics of Chlorofluorocarbon (CFC) Machine Replacement

DTIC Science & Technology

1994-09-01

trichloroethane (methyl chloroform) CC13CH 3 133.4 74 165 1 41b I , 1 -dichloro- 1 -fluoroothane CC12FCH 3 117.0 32 90 142b I1-chloro- 1 . 1 - difluoroethans ... 1 Introduction... 1 Impact On The Commercial And Industrial Sectors

16 CFR 1401.1 - Scope.

Code of Federal Regulations, 2011 CFR

2011-01-01

... Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS SELF PRESSURIZED... Product Safety Act (15 U.S.C. 2076(e)) for marketers and importers of self-pressurized consumer products... product stating that it contains a chlorofluorocarbon that may harm the public health and environment by...

16 CFR 1401.1 - Scope.

Code of Federal Regulations, 2012 CFR

2012-01-01

... Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS SELF PRESSURIZED... Product Safety Act (15 U.S.C. 2076(e)) for marketers and importers of self-pressurized consumer products... product stating that it contains a chlorofluorocarbon that may harm the public health and environment by...

16 CFR 1401.1 - Scope.

Code of Federal Regulations, 2014 CFR

2014-01-01

... Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS SELF PRESSURIZED... Product Safety Act (15 U.S.C. 2076(e)) for marketers and importers of self-pressurized consumer products... product stating that it contains a chlorofluorocarbon that may harm the public health and environment by...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Emission Limits for Hydrogen Halide and..., Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

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.

Stratospheric Ozone destruction by the Bronze-Age Minoan eruption (Santorini Volcano, Greece)

PubMed Central

Cadoux, Anita; Scaillet, Bruno; Bekki, Slimane; Oppenheimer, Clive; Druitt, Timothy H.

2015-01-01

The role of volcanogenic halogen-bearing (i.e. chlorine and bromine) compounds in stratospheric ozone chemistry and climate forcing is poorly constrained. While the 1991 eruption of Pinatubo resulted in stratospheric ozone loss, it was due to heterogeneous chemistry on volcanic sulfate aerosols involving chlorine of anthropogenic rather than volcanogenic origin, since co-erupted chlorine was scavenged within the plume. Therefore, it is not known what effect volcanism had on ozone in pre-industrial times, nor what will be its role on future atmospheres with reduced anthropogenic halogens present. By combining petrologic constraints on eruption volatile yields with a global atmospheric chemistry-transport model, we show here that the Bronze-Age ‘Minoan’ eruption of Santorini Volcano released far more halogens than sulfur and that, even if only 2% of these halogens reached the stratosphere, it would have resulted in strong global ozone depletion. The model predicts reductions in ozone columns of 20 to >90% at Northern high latitudes and an ozone recovery taking up to a decade. Our findings emphasise the significance of volcanic halogens for stratosphere chemistry and suggest that modelling of past and future volcanic impacts on Earth’s ozone, climate and ecosystems should systematically consider volcanic halogen emissions in addition to sulfur emissions. PMID:26206616

Stratospheric Ozone destruction by the Bronze-Age Minoan eruption (Santorini Volcano, Greece).

PubMed

Cadoux, Anita; Scaillet, Bruno; Bekki, Slimane; Oppenheimer, Clive; Druitt, Timothy H

2015-07-24

The role of volcanogenic halogen-bearing (i.e. chlorine and bromine) compounds in stratospheric ozone chemistry and climate forcing is poorly constrained. While the 1991 eruption of Pinatubo resulted in stratospheric ozone loss, it was due to heterogeneous chemistry on volcanic sulfate aerosols involving chlorine of anthropogenic rather than volcanogenic origin, since co-erupted chlorine was scavenged within the plume. Therefore, it is not known what effect volcanism had on ozone in pre-industrial times, nor what will be its role on future atmospheres with reduced anthropogenic halogens present. By combining petrologic constraints on eruption volatile yields with a global atmospheric chemistry-transport model, we show here that the Bronze-Age 'Minoan' eruption of Santorini Volcano released far more halogens than sulfur and that, even if only 2% of these halogens reached the stratosphere, it would have resulted in strong global ozone depletion. The model predicts reductions in ozone columns of 20 to >90% at Northern high latitudes and an ozone recovery taking up to a decade. Our findings emphasise the significance of volcanic halogens for stratosphere chemistry and suggest that modelling of past and future volcanic impacts on Earth's ozone, climate and ecosystems should systematically consider volcanic halogen emissions in addition to sulfur emissions.

Delayed myelosuppression with acute exposure to hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and environmental degradation product hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) in rats.

PubMed

Jaligama, Sridhar; Kale, Vijay M; Wilbanks, Mitchell S; Perkins, Edward J; Meyer, Sharon A

2013-02-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a widely used munitions compound, and hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), its N-nitroso product of anaerobic microbial nitroreduction, are contaminants of military sites. Previous studies have shown MNX to be the most acutely toxic among the nitroreduced degradation products of RDX and to cause mild anemia at high dose. The present study compares hematotoxicity with acute oral exposure to MNX with parent RDX. Both RDX and MNX caused a modest decrease in blood hemoglobin and ~50% loss of granulocytes (NOAELs=47 mg/kg) in female Sprague-Dawley rats observed 14 days post-exposure. We explored the possibility that blood cell loss observed after 14 days was delayed in onset because of toxicity to bone marrow (BM) progenitors. RDX and MNX decreased granulocyte/macrophage-colony forming cells (GM-CFCs) at 14, but not 7, days (NOAELs=24 mg/kg). The earliest observed time at which MNX decreased GM-CFCs was 10 days post-exposure. RDX and MNX likewise decreased BM burst-forming units-erythroid (BFU-Es) at 14, but not 7, days. Granulocyte-erythrocyte-monocyte-megakaryocyte (GEMM)-CFCs were unaffected by RDX and MNX at 7 days suggesting precursor depletion did not account for GM-CFC and BFU-E loss. MNX added to the culture media was without effect on GM-CFC formation indicating no direct inhibition. Flow cytometry showed no differential loss of BM multilineage progenitors (Thy1.1(+)) or erythroid (CD71(+)) precursors with MNX suggesting myeloid and erythroid lineages were comparably affected. Collectively, these data indicate that acute exposure to both RDX and MNX caused delayed suppression of myelo- and erythropoiesis with subsequent decrease of peripheral granulocytes and erythrocytes. Copyright © 2012 Elsevier Inc. All rights reserved.

Application of δ18O, δD, 3H-3He and CFCs to characterize the nitrate contamination of groundwater in Eumsung, Korea

NASA Astrophysics Data System (ADS)

Ju, Y. J.; Kaown, D.; Hahm, D.; Kim, I.; Lee, S. S.; Koh, E. H.; Kim, M.; Yoon, Y. Y.; Lee, K. K.

2015-12-01

We measured the major ions, stable oxygen and hydrogen isotopes, 3H-3He and CFCs concentration in groundwater to identify the characteristics of nitrate contamination and to understand the groundwater recharge patterns. In this study, 17 groundwater samples were collected for 5days (from March 3rd to 7th, 2015) in Eumseong, Korea. In the study area, NO3- concentrations in some groundwater samples (16 of 17) ranged from 5.7 to 103.7 mg/L (avg. 43.3 mg/L), which were substantially higher than the drinking water quality standard (10 mg/L). These excess NO3- inputs in groundwater seem to be originated from the agricultural use of chemical fertilizers because major ions associated with fertilizers were significantly correlated with NO3-. It seems that major groundwater recharge event during monsoon season is highly probable from the analysis of δ18O and δD. The apparent groundwater age using 3H-3He and CFCs varies from 5 to 40 yrs although the study area is small (1 km2). For the samples showed large deficiency of 3He, the sensitivity analysis was performed using NOBLE 90 in an effort to quantify the degassed amount. Since nitrate sources are quite evenly distributed through the field site, groundwater ages from shallow aquifer is inversely correlated with the nitrate concentrations. Our result implies that the 3H-3He ratio can be a useful indicator of tracing the recharge pattern of groundwater but also the nitrate loading characteristic in a small scale agricultural area. Acknowlegments: Financial support was provided by the "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003) and the research project of "Advanced Technology for Groundwater Development and Application in Riversides (Geowater+)" in "Water Resources Management Program (code 11 Technology Innovation C05)" of the MOLIT and the KAIA in Korea.

End-product quality characteristics and consumer response of chickpea flour-based gluten-free muffins containing corn starch and egg white.

PubMed

Alvarez, María Dolores; Herranz, Beatriz; Jiménez, María José; Canet, Wenceslao

2017-12-01

The objective of this work was to study changes in technological characteristics and sensory properties of gluten-free muffins when using chickpea flour (CF) alone and/or with partial CF replacement by corn starch (CS). The effect of partial whole egg replacement by egg white (EW) was also investigated. Four different CF:CS ratios (100:0, 75:25, 50:50, and 25:75) were used in formulations with and without incorporated EW, and compared with wheat flour (WF) muffins (0:0). Muffins prepared from CF alone had lower hardness, springiness, cohesiveness, chewiness, and resilience than control ones. However, reducing protein content by CS addition significantly increased texture profile analysis parameters of muffin crumb. Muffins prepared with 25:75 ratio had a structure with springiness similar to muffins made with WF but were too hard. Reducing whole egg content by partial replacement with EW also significantly increased muffin hardness. Flash profile performed by consumers showed a clear discrimination of muffins according to CF:CS ratio. Muffins containing both CF and CS at 50:50 ratio had the same high overall acceptability and purchase intention as gluten ones. Gluten-free CF-based muffins of satisfactory quality can be manufactured by CS incorporation, either with or without EW. By decreasing and increasing protein and starch contents of chickpea flour (CF) by incorporation of corn starch (CS), muffins formulated from a combination of CF and CS at different CF:CS ratios, either with or without partial replacement of whole egg with egg white, result in high-quality muffins with similar technological and sensory characteristics to those of their gluten counterparts. Sensory overall acceptability and purchase intention of muffins made with a 50:50 ratio did not differ significantly from those of the controls. These findings will benefit celiac population, while promoting the value and utilization of pulses through muffins. © 2017 Wiley Periodicals, Inc.

Apparent CFC and 3H/ 3He age differences in water from Floridan Aquifer springs

NASA Astrophysics Data System (ADS)

Happell, James D.; Opsahl, Stephen; Top, Zafer; Chanton, Jeffrey P.

2006-03-01

The apparent CFC-11, -12 and -113 ages of Upper Floridan Aquifer water discharged from 31 springs located in Florida and Georgia ranged from 11 to 44 years when samples were collected in 2002 and 2003. Apparent 3H/ 3He ages in these springs ranged from 12 to 66 years. Some of the springs sampled did not yield valid CFC ages because one or more of the CFCs were contaminated by non-atmospheric sources. Of the 31 springs sampled, six were contaminated with all three CFCs and nine were contaminated with one or two CFCs. Of the remaining 16 springs, the CFC distributions of four could be modeled assuming a single source of water, and 11 were best modeled by assuming two sources of water, with one of the water sources >60 years old. The CFC and 3H/ 3He apparent ages and the simple mixing models applied to these ages suggest that past impacts to the water quality of water recharging the sampled springs may take anywhere from 0 to ˜60 years or more to appear in the discharging spring water. In 27 springs where both 3H/ 3He ages and CFC ages were available, five springs gave similar results between the two techniques, while in the other 22 cases the 3H/ 3He apparent ages were 8-40 years greater than the CFC ages. Large excesses of 4He were observed in many of the springs, consistent with a source of older water. This older water may also carry an additional and unaccounted for source of 3He, which may be responsible for the greater 3H/ 3He ages relative to the CFC ages. We believe that the large excess 3He and 4He values and apparent age differences are related to regional climate variations because our samples were obtained at the end of a 4-year drought.

Carcinogenicity of by-products of disinfection in mouse and rat liver

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

Herren-Freund, S.L.; Pereira, M.A.

1986-11-01

By-products of disinfection were tested for initiating and/or promoting activity in rat liver by using the rat liver foci bioassay. The assay uses an increased incidence of ..gamma..-glutamyltranspeptidase-positive foci (GGT foci) as an indicator of carcinogenicity. The by-products of disinfection, including chloramine, halogenated humic acids, halogenated ethanes, halogenated acetonitriles, halogenated methanes, halogenated ethylene, and N-Cl piperidine, did not initiate GGT foci, which would indicate that they are not capable of initiating carcinogenesis. Chloroform and halogenated benzenes were tested in this assay for their ability to promote the occurrence of GGT foci and tumors initiated by diethylnitrosamine (DENA). Chloroform either hadmore » no effect or inhibited the occurrence of GGT foci when administered subsequent to a single dose of DENA. However, when the chloroform was administered in drinking water concurrently with weekly doses of DENA, it enhanced the formation of liver tumors. Of 20 halogenated benzenes tested, only 1,2,4,5-tetrachlorobenzene and hexachlorobenzene promoted the occurrence of DENA-initiated GGT foci. Thus in rat liver, the tested by-products of drinking water disinfection did not demonstrate tumor-initiating activity, although a few appeared to possess tumor-promoting activity. Chloroform was also tested for tumor-promoting activity in 15-days-old Swiss mice initiated with ethylnitrosourea (ENU). ENU at 5 and 20 ..mu..g/g caused a dose-dependent increase in liver tumors. In male mice, chloroform inhibited both spontaneous and ENU-induced liver tumors. When administered in the drinking water, chloroform inhibited, whereas phenobarbital promoted, hepatocarcinogenesis in mice.« less

13C and 19F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles.

PubMed

Szell, Patrick M J; Gabriel, Shaina A; Gill, Russell D D; Wan, Shirley Y H; Gabidullin, Bulat; Bryce, David L

2017-03-01

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P2 1 /c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 13 H 9 N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 12 H 8 N 2 , and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 8 H 12 N 2 . 13 C and 19 F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from 19 F to 13 C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional 1 H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental 13 C and 19 F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

Tropospheric chemistry research in the U.S.: 1991-1994

NASA Astrophysics Data System (ADS)

Penner, Joyce E.; Atherton, Cynthia S.; Dignon, Jane

1995-07-01

The troposphere is chemically complex. Many of the important species in the troposphere are short-lived, with lifetimes less than or of order of a month. Hence, the composition of the troposphere is regionally diverse, leading to regionally diverse chemical processes which control that composition. With the advent of three-dimensional models and regionally-specific estimates of emissions, however, it has become clear that human activity has perturbed the composition of even short-lived species over vast regions of the globe. The list of short-lived species of concern includes the reactive nitrogen oxides, reactive sulfur, ozone, nonmethane hydrocarbons and carbon monoxide. Observations have established that increases in the long-lived species such as carbon dioxide, methane, nitrous oxide, and the chlorofluorocarbons are taking place with important resulting impacts on stratospheric chemistry. Further, there is some indication that carbonyl sulfide (a major precursor to stratospheric aerosols) may have an important anthropogenic source. Growth of pollutants such as these are of concern because they act as greenhouse gases or aerosol precursors (CO2, CH4, O3, N2O, chlorofluorocarbons, carbonyl sufide, reactive sulfur), as agents for depletion of stratospheric ozone (N2O, chlorofluorocarbons), are harmful to vegetation (O3, acids) or act as nutrients (nitrate, sulfate, trace metals). The chemical interactions are important to understand, because the build up of pollutants depends not only on the rates of their release into the troposphere but on their rate of removal in the troposphere. Removal rates depend on processes which determine the rate of oxidation of the component (which for most species proceeds mainly by reaction with the hydroxyl radical) or through precipitation scavenging or dissolution in the ocean (which requires that the pollutant or its oxidation product(s) be soluble in water).

Chlorofluorocarbon and tritium age determination of ground-water recharge in the Ryan Flat subbasin, Trans-Pecos Texas

USGS Publications Warehouse

Bartolino, J.R.

1997-01-01

A study was conducted to determine the relative influence of mountain-front infiltration in the Ryan Flat subbasin and to determine whether recent recharge (post-1940), which is of importance to water-use planning, has reached the Salt Basin aquifer, Trans-Pecos Texas. The alluvial and volcanic Salt Basin aquifer lies within a bolson, and the average depth to water in most of the subbasin is approximately 250 feet. Concentrations of the chlorofluorocarbons CFC-11, CFC-12, and CFC-113, as well as tritium, were measured in water from 10 wells in the study area. CFC-model recharge dates ranged from pre-1940 to the early 1970's. Ground water in five wells had CFC-model dates of pre-1940 or pre-1945. Ground water in two wells had dates of the mid- to late 1940's. Ground water from one well had a CFC-model recharge age of the early 1950's. Samples from the remaining two wells were most probably contaminated in some manner and are probably unreliable. CFC-model ages were calculated independently for the three chlorofluorocarbons, though the presence of volatile organic compounds affected agreement among them. Tritium activities in the nine wells for which tritium was analyzed indicated pre-1953 recharge and thus agreed approximately with the CFC-model dates. Ground water was analyzed for selected water-quality constituents. Water from all wells met U.S. Environmental Protection Agency national primary and secondary drinking water standards for all tested constituents except fluoride in samples from three wells. Silica concentrations in water from six wells exceeded a range considered typical in natural waters.

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 and chemistry of these enzymes. In particular, the latest crystallographic snapshots of active site architecture and halide binding sites have provided key insights into enzyme catalysis. Herein is a summary of the five classes of halogenases, focusing on the three most recently discovered: flavin-dependent halogenases, non-heme iron-dependent halogenases, and nucleophilic halogenases. Further, the potential roles of halide-binding sites in determining halide selectivity are discussed, as well as whether or not binding-site composition is always a seminal factor for selectivity. Expanding our understanding of the basic chemical principles that dictate the activity of the halogenases will advance both biology and chemistry. A thorough mechanistic analysis will elucidate the biological principles that dictate specificity, and the application of those principles to new synthetic techniques will expand the utility of halogenations in small-molecule development. PMID:18774824

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.

Nontypical iodine–halogen bonds in the crystal structure of (3 E )-8-chloro-3-iodomethylidene-2,3-dihydro-1,4-oxazino[2,3,4- ij ]quinolin-4-ium triiodide

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

Bartashevich, E. V.; Batalov, V. I.; Yushina, I. D.

2016-04-29

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C 12H 8ClINO +·I 3 -, described by X-ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. Lastly, the influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.

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).

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.

The Two Faces of Ozone.

ERIC Educational Resources Information Center

Monastersky, Richard

1989-01-01

Provides answers to questions regarding the ozone problem: (1) nature of ozone in the troposphere and stratosphere; (2) possibility of sending the excess ozone at ground level to the stratosphere; (3) possibility of producing pure ozone and carrying it to the stratosphere; and (4) banning chlorofluorocarbons. (YP)

ULTRASONIC CLEANING AS A REPLACEMENT FOR A CHLORO- FLUOROCARBON-BASED SYSTEM

EPA Science Inventory

This report describes the technical and economic evaluation of the replacement of a vapor degreasing system with an ultrasonic cleaning system to clean stainless steel components. Heated inorganic water-based cleaning fluid was utilized in lieu of a chlorofluorocarbon (CFC, freon...

Tending the Global Commons.

ERIC Educational Resources Information Center

Ember, Lois R.; And Others

1986-01-01

Discusses the global trends associated with the increasing levels of carbon dioxide, nitrous oxide, methane, and chlorofluorocarbons (CFS) in the earth's atmosphere. Presents several ecological effects associated with these increases, along with some of the possible social and economic implications for the quality of life. Argues for more…

NEW CHEMICAL ALTERNATIVE FOR OZONE-DEPLETING SUBSTANCES: HFC-245CA

EPA Science Inventory

The report gives results of a preliminary evaluation of a new hydrofluorocarbon (HFC) -- HFC-245ca or 1,1,2,2,3-pentafluoropropane -- as a possible alternative for chlorofluorocarbon (CFC)-11 (trichlorofluoromethane) and hydrochlorofluorocarbon (HCFC)-123 (1,1,1-trifluoro-2,2-dic...

16 CFR § 1401.1 - Scope.

Code of Federal Regulations, 2013 CFR

2013-01-01

... Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION CONSUMER PRODUCT SAFETY ACT REGULATIONS SELF... Product Safety Act (15 U.S.C. 2076(e)) for marketers and importers of self-pressurized consumer products... product stating that it contains a chlorofluorocarbon that may harm the public health and environment by...

Reference Fluid Thermodynamic and Transport Properties Database (REFPROP)

National Institute of Standards and Technology Data Gateway

SRD 23 NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) (PC database for purchase)   NIST 23 contains revised data in a Windows version of the database, including 105 pure fluids and allowing mixtures of up to 20 components. The fluids include the environmentally acceptable HFCs, traditional HFCs and CFCs and 'natural' refrigerants like ammonia

Interactions between volatile organic compounds and reactive halogen in the tropical marine atmosphere using WRF-Chem

NASA Astrophysics Data System (ADS)

Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; von Glasow, Roland

2016-04-01

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 cause ozone (O3) destruction, 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. There are indications that the chemistry of reactive halogens and oxygenated VOCs (OVOCs) in the tropics are inter-related. Moreover, the presence of aldehydes, such as glyoxal (CHOCHO), has a potential impact on radical cycling and secondary organic aerosol (SOA) formation in the MBL and free troposphere (FT). Model calculations suggest aldehydes to be an important sink for bromine atoms and hence competition for their reaction with O3 forming BrO and so illustrating a link between the cycles of halogens and OVOCs in the marine atmosphere. The main objective of this contribution is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens and OVOCs and their links using the latest version of the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. WRF-Chem is a highly flexible community model for atmospheric research where aerosol-radiation-cloud feedback processes are taken into account. Our current reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. The MOZART mechanism includes detailed gas-phase chemistry of CHOCHO formation as well as state-of-the-science pathways to form SOA. Oceanic emissions of aldehydes, including CHOCHO, and of organic halogens based on measurements from the TORERO campaign have been added into the model. 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 an evaluation of the relevant tropospheric gas-phase chemistry (O3, H2O), inorganic halogen species (BrO, IO), aldehydes (CH3CHO, CHOCHO) and Very Short Lived Halocarbons (VSLH).

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 that the observed decrease in 4-aminophenol formation was accompanied by a metabolic switch to 2-aminophenols and N-hydroxyanilines, while products resulting from NIH-type mechanisms were not observed. For a C4-chloro-, bromo-, or iodo-substituted 2-fluoroaniline the Vmax for the oxidative dehalogenation was reduced by the additional electron withdrawing fluorine substituent at the C2 position in a similar way.(ABSTRACT TRUNCATED AT 400 WORDS)

A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

NASA Astrophysics Data System (ADS)

Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H.

2003-09-01

A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.

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

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.