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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Absolute infrared band strength measurement of the ClO radical by Fourier transform infrared spectroscopy

High-resolution (0.005/cm) FTIR spectra of the X2Pi(i)-X2Pi(i) (1-0) rovibrational bands of (C-35)(O-16) and (Cl-37)(O-16) were obtained in 1 torr of helium carrier gas. After measuring the strengths of approximately 830 individual IR lines from several spectra, a total band strength of 13.1 + or - 1.1/sq cm atm and a first Herman-Wallis coefficient of (4.12 + or - 0.62) x 10 to the -3rd were determined.

Lang, Valerie I.↗
NASA NTRS2001

In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

Anderson, James G.↗
NASA NTRS2005

Chemistry, Dynamics, and Radiation of Ozone Loss: Airborne Measurements of OH, HO2, NO2, ClO, BrO, IO, ClONO2, BrONO2, ClOOCl, and H2O

This grant continued the research initially funded under NAG1-01095. This research addresses, through a combination of in situ and remote aircraft-borne instruments, the following scientific questions: Which mechanisms are responsible for the continuing erosion of ozone over midlatitudes of the Northern Hemisphere? Will the rapid loss of ozone over the Arctic in late winter continue to worsen over the next two decades? Are these large losses dynamically coupled to midlatitudes? Which mechanisms dictate the rate of exchange of material between the troposphere and stratosphere? How will these processes change in response to changes in climate? Will regional scale pollution episodes, that are emerging as predictable seasonal events, significantly affect the middle-to-upper troposphere chemical composition. If so, how will these changes alter the chemical composition of the middle world? What changes are predicted for the overworld? Why has the arctic stratosphere become colder in the late winter phase in recent years? Have increases in tropical upper troposphere temperatures increased the temperature gradient such as to change the trajectories of vertically propagating waves, thus reducing the effectiveness of the meridional circulation for transport of heat, momentum and ozone from the tropics to high latitudes?

Anderson, James G.↗
DOE OSTI2022

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO 4 - ) has synthetic and natural sources. Synthetic ClO 4 - is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO 4 - in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO 4 - that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine ( 37 Cl/ 35 Cl) and oxygen ( 18 O/ 16 O, 17 O/ 16 O) and the isotopic abundance of radioactive 36 Cl in ClO 4 - can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO 4 - collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. We report isotopic data indicate that indigenous natural ClO 4 - was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO 4 - was present in the three remaining wells with natural ClO 4 - , and a minor fraction of Atacama-fertilizer-derived ClO4- was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO 4 - has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO 4 - in groundwater by flushing accumulated salts from the unsaturated zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Evolution of chemically processed air parcels in the lower stratosphere

Aircraft, ground-based, and satellite measurements indicate large concentrations of ClO in the lower stratosphere in and near the polar vortex. The amount of local ozone depletion caused by these large ClO concentrations will depend on the relative rates of ozone loss and ClO recovery. ClO recovery occurs when NO(x), from HNO3 photolysis, reacts with ClO to form ClONO2. We show that air parcels with large amounts of ClO will experience a subsequent ozone depletion that depends on the solar zenith angle. When the solar zenith angle is large in the middle of winter, the recovery of the ClO concentration in the parcel is slow relative to ozone depletion. In the spring, when the solar zenith angle is smaller, the ClO recovery is much faster. After ClO recovery, the chlorine chemistry has not returned to normal. The ClO has been converted to ClONO2. ClO production from further encounters with PSCs will be limited by the heterogeneous reaction of ClONO2 with water. Large ozone depletions, of the type seen in the Antarctic, occur only if there is significant irreversible denitrification in the air parcel.

Stolarski, Richard S.↗
DOE OSTI2022

Dinuclear Complexes of Uranyl, Neptunyl, and Plutonyl: Structures and Oxidation States Revealed by Experiment and Theory

Dinuclear perchlorate complexes of uranium, neptunium, and plutonium were characterized by reactivity and DFT, with results revealing structures containing pentavalent, hexavalent, and heptavalent actinyls, and actinyl-actinyl interactions (AAIs). Electrospray ionization produced native complexes [(AnO 2 ) 2 (ClO 4 ) 3 ] - for An:An = U:U, Np:Np, Pu:Pu, and Np:Pu, which are intuitively formulated as actinyl(V) perchlorates. However, DFT identified lower-energy structures [(AnO 2 )(AnO 3 )(ClO 4 ) 2 (ClO 3 )] - comprising a perchlorate fragmented to ClO 3 , actinyl(VI) cation An VI O 2 2+ , and neutral AnO 3 . For U:U and Np:Np, and Np in Np:Pu, the coordinated AnO 3 is calculated as actinyl(VI) with an equatorial oxo, [O yl =An VI =O yl ][=O eq ], whereas for Pu:Pu, it is plutonyl(V) oxyl, [O yl =Pu V =O yl ][-O eq • ]. The implied lower stability of Pu VI versus Np VI indicates weaker Pu=O eq versus Np=O eq bonding. Adsorption of O 2 by the U:U complex suggests oxidation of U V to U VI , corroborating the assignment of perchlorate [(An V O 2 ) 2 (ClO 4 ) 3 ] - . DFT predicts the O 2 adducts are [(An VI O 2 )(O 2 )(An VI O 2 )(ClO 4 ) 3 ] - with actinyls oxidized from +V to +VI by bridging peroxide, O 2 2- . In accordance with reactivity, O 2- addition is computed as substantially exothermic for U:U and least favorable for Pu:Pu. Collision-induced dissociation of native complexes eliminated ClO 2 to yield [(AnO 2 )(O) 2 (AnO 2 )(ClO 4 ) 2 ] - , in which fragmented O atoms bridge as oxyl O -• and oxo O 2- to yield uranyl(VI) and plutonyl(VI), or as oxos O 2- to yield neptunyl(VII), [O yl =Np VII =O yl ] 3+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Chlorine Deactivation in the Lower Stratospheric Polar Regions during late Winter: Results from UARS

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

Santee, M. L.↗
NASA NTRS1982

Is there any chlorine monoxide in the stratosphere?

A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.

Rogers, J. D.↗
NASA NTRS1992

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗
NASA NTRS1994

Arctic chlorine monoxide observations during spring 1993 over Thule, Greenland, and implications for ozone depletion

We have determined the vertical distribution of chlorine monoxide (ClO), from measurements of pressure-broadened molecular-emission spectra made over Thule, Greenland, during the 1993 Arctic spring. The measurements show a weak lower stratospheric layer of chlorine monoxide inside the vortex in late February, which was, however, significantly greater in mixing ratio than that seen in observations we made in the spring of 1992. ClO was also observed in much smaller quantities in early to mid-March 1993 when Thule was outside the vortex. The amount of ClO within the vortex was severely reduced by the time it returned over Thule in late March. This reduction occurred several weeks earlier relative to the winter solstice than the decline of ClO inside the Antarctic vortex in 1993. The enhanced Arctic lower stratospheric layer seen in late February 1993 at a nearly equivalent photochemical period, and beyond. We have calculated daily ozone loss rates, due primarily to the dimer chlorine catalytic cycle, from both sets of measurements. The vertical integral of the Arctic daily percentage ozone loss when the largest ClO levels were present, at the end of February, is found to be approximately one quarter of that in the Antarctic at a photochemical period only 1 week later. The relative weakness of daily ozone depletion, combined with the early disappearance of ClO in the Arctic, suggests that hemispheric dilution by ozone-poor air from within the Arctic vortex is unlikely to be sufficient to explain the historically extreme loss of midlatitude northern hemisphere ozone which began in 1992 and persisted throughout 1993.

Shindell, D. T.↗
DOE OSTI2025

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision‐Induced Dissociation

The infrared multiphoton dissociation spectrum of the gas-phase uranyl perchlorate anion ([UO 2 (ClO 4 ) 3 ] − ) was measured. Here, the asymmetric uranyl stretch lies somewhere between 930 and 1030 cm −1 , though it could not be deconvoluted from a closely located perchlorate stretching mode. The experimentally measured spectrum was in good agreement with spectra calculated using density functional theory with the B3LYP and TPSSh functionals and Grimme's D3 dispersion corrections with Becke–Johnson damping. The calculations suggest that the asymmetric uranyl stretch lies in the range of 970–980 cm −1 , about 20–30 cm −1 higher than for the analogous uranyl trinitrato complex and consistent with perchlorate as a weaker ligand than nitrate. Like the uranyl trinitrato anion, fragmentation of [UO 2 (ClO 4 ) 3 ] − by collision-induced dissociation resulted in loss of a ClO 3 • radical to form [UO 3 (ClO 4 ) 2 ] − . Infrared multiphoton dissociation measurements of [UO 3 (ClO 4 ) 2 ] − indicate that the structure of the product ion has an O − ligand bound to the uranyl in a T-arrangement and two perchlorate ligands, matching the findings from uranyl nitrato complexes. The uranyl stretch in this complex was slightly separated from the perchlorate modes and was measured at 906 cm −1 , slightly higher than for the analogous nitrate complex, again consistent with perchlorate as a weaker ligand than nitrate in the gas phase.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2023

Combined chlorine dioxide–membrane distillation for the treatment of produced water

Membrane distillation (MD) is a promising technique for desalinating hypersaline brine, such as produced water (PW). To date, fouling and scaling have remained as major challenges for MD implementation. In this study, chlorine dioxide combined with induced air floatation (ClO 2 -IAF) was systematically investigated as a pretreatment prior to MD. First, the ClO 2 generation based on sodium chlorite and hydrochloric acid was optimized to maximize the on-demand ClO 2 production. The maximum production yield of 18.4% was obtained with 4wt.% NaClO 2 and 20wt.% HCl solutions, with a molar ratio of 1:1.25. Then, two real PW samples were pretreated, and removal efficiencies for total suspended solids (TSS), turbidity, iron, and total organic carbon (TOC) were comprehensively studied by varying the ClO 2 dosage between 6 and 91 mg/L. The ClO 2 -IAF pretreatment displayed TSS and turbidity removals above 90% and TOC removal close to 55%. Further, the PW constituents such as benzene, toluene, ethylbenzene, xylene (BTEX), and total petroleum hydrocarbons (TPH) were analyzed and quantified throughout the cascade of the treatments. The volatiles like BTEX were mainly removed by air floatation, while saturated hydrocarbons such as TPH were retained by the hydrophobic membrane. The MD long-term stability without any in-place cleaning was evaluated, and the membrane withstood for twenty two days without wetting, suggesting that optimizing oxidation pretreatment is critical for mitigating the fouling in MD. Results suggest that organic fouling in PW could be effectively reduced by the pretreatment, but further treatment is required to mitigate the scaling, which resulted in MD wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Infrared line intensities of chlorine monoxide

Absolute infrared line intensities of several ClO lines in the rotational-vibrational (1-0) band were measured using infrared heterodyne spectroscopy near 12 microns. A measurement technique using combined ultraviolet absorption and infrared line measurements near 9.5 microns and 12 microns permitted an accurate determination of the column densities of O3 and ClO in the absorption cell and thus improved ClO line intensities. Results indicate ClO line and band intensities approximately 2.4 times lower than previous experimental results. Effects of possible failure of local thermodynamic equilibrium conditions in the absorption cell and the implication of the results for stratospheric ClO measurements in the infrared are discussed.

Kostiuk, T.↗
NASA NTRS1986

Chlorine chemistry in the Antarctic stratosphere - Impact of OClO and Cl2O2 and implications for observations

Theories have been proposed to relate the reduction of O3 during Antarctic spring to catalytic cycles involving chlorine and bromine species. A necessary condition for any chlorine-catalyzed scheme is that a large fraction of the chlorine must be in the form of ClO in the lower stratosphere. It has been suggested that these high levels of ClO could be maintained by fast heterogeneous reactions, whose rates are not known at present. Model calculations based on the above mechanisms predict considerable amounts of OClO and Cl2O2, particularly during the night. Results of calculations of the diurnal variations of ClO, OClO, and Cl2O2 during Antarctic spring are presented for different cases. Results from the calculations suggest that coincident measurements of the total column abundance and diurnal variation of ClO and OClO may help constrain key aspects of the proposed chemical mechanisms. Removal of O3 by the catalytic cycle involving Cl2O2 could be as important as that involving BrO for present levels of chlorine, provided that Cl2O2 photolyzes rapidly to yield Cl and ClO2. It is shown that there is no synergy between these two cycles, since they both compete for the available ClO.

Rodriguez, Jose M.↗
NASA NTRS1994

The response of C1O radical concentrations to variations in NO2 radical concentrations in the lower stratosphere

The respose of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of (ClO), (NO), (NO2) and (O3) in the midlatitude lower stratosphere. This analysis demonstrates that (ClO) is inversely correlated with (NO2), consistent with formation and photolysis of (ClONO2). A factor of ten range in the concentration if NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cu cm), with a comparable range in the ratio of (ClO) to total available inorganic chlorine (1% less than or equal to (ClO)/(Cl(sub y)) less than or equal to 5%. This analysis leads to an estimate of (ClONO2)/(Cl(sub y)) = 0.12 (x/2), in the mid-latitude, lower-stratospheric air masses sampled.

Stimfle, R. M.↗