Variability of bromine monoxide at Barrow, Alaska, over four halogen activation (March–May) seasons and at two on‐ice locations
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Peter K. Peterson↗
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Application of Satellite‐Based Detections of Arctic Bromine Explosion Events Within GEOS‐Chem
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P. A. Wales↗
Intercomparison Between Surrogate, Explicit, and Full Treatments of VSL Bromine Chemistry Within the CAM‐Chem Chemistry‐Climate Model
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Rafael P. Fernandez↗
Convective Transport of Very-short-lived Bromocarbons to the Stratosphere
We use the NASA GEOS Chemistry Climate Model (GEOSCCM) to quantify the contribution of two most important brominated very short-lived substances (VSLS), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLS from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the Western Pacific warm pool, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies ∼8 ppt total bromine to the base of the Tropical Tropopause Layer (TTL, ∼150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (∼7.8-8.4 ppt) in the above active convective lofting regions. Of the total ∼8 ppt VSLS-originated bromine that enters the base of TTL at ∼150 hPa, half is in the form of source gas injection (SGI) and half as product gas injection (PGI). Only a small portion (< 10%) the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On global and annual average, CHBr3 and CH2Br2, together, contribute ∼7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep convection strength between maximum and minimum convection conditions can introduce a ∼2.6 pptv uncertainty in the contribution of VSLS to inorganic bromine in the stratosphere (BryVSLS). Contrary to the conventional wisdom, minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, thus a significant increase in PGI (2-3 ppt), greatly exceeds the relative minor decrease in SGI (a few 10ths ppt.
bromine↗
NASA Research on the Hydrodynamics of the Gaseous Vortex Reactor
The experimental and analytical results to date of a study of a two-component gaseous vortex system are presented in this paper. Analytical expressions for tangential velocity and static-pressure profiles in a turbulent vortex show good agreement with experimental data. Airflow rates from 0.075 to 0.14 pound per second and corresponding tangential velocities from 160 to 440 feet per second are correlated by turbulent Reynolds numbers from 1.95 to 2.4. An analysis of an air-bromine gas mixture in a turbulent vortex indicates that a boundary value of bromine-to-air radial velocity ratio (u(2)/u(1)) of 0.999 gives essentially no bromine buildup, while a value of 0.833 results in considerable separation. For a constant value of (u(2)/u(1))(0) the bromine buildup increases as (1) the tangential velocity increases, (2) the air-to-bromine weight-flow ratio decreases, (3) the airflow rate decreases, (4) the temperature decreases, and (5) the turbulence decreases. Analytical temperature, pressure, and tangential-velocity profiles are also presented. Preliminary experimental results indicate that the flow of an air-bromine mixture through a vortex field results in a bromine density increase to a maximum value; followed by a decrease; the air density exhibits a uniform decrease from the outer vortex radius to the exhaust-nozzle radius.
Ragsdale, Robert G.↗
Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2
Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (Br~SLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to ~ 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only accounts for ~0.2 pptv (4%) difference in inorganic bromine delivered to the stratosphere.
Liang, Q.↗
Degradation of Intercalated Graphite Epoxy Composites Exposed to Low Earth Orbit
Four different graphite fiber/epoxy composites were exposed to the wake-side low Earth orbit (LEO) environment on the Optical Reflector Materials Experiment III (ORMatE-III) platform mounted on the exterior of the ISS for two years in order to determine their long term durability in the space environment. Three of the composite samples used bromine intercalated P100 fibers and one used pristine P100 fibers. One of the P100-Br samples was coated with a protective SiO2 layer, and half of another was coated with SiO2. Results were compared with the EOIM-III experiment which exposed the same materials in LEO in the ram direction for 42 h on the Space Shuttle. Although the atomic oxygen (AO) fluence of the ORMatE-III samples was one-third of the EOIM-III exposure, the resulting effects were qualitatively the same. Both found that SiO2 coated intercalated graphite composites showed no AO erosion, verifying that conventional protection strategies are applicable to bromine intercalated composites. Both found that bromine intercalation does not alter the AO erosion rates of graphite fiber/epoxy composites. Both found no bromine was detected to have migrated into the surrounding epoxy, even for highly eroded fibers and epoxy, allaying fears that bromination could compromise the properties of the epoxy. And both found no corrosive bromine was detected to have been released by the fibers allaying fears that outgassing could degrade sensitive electronics. The uncoated EOIM-III samples suffered slightly greater erosion resulting in a slightly higher solar absorptance. The general conclusion is that ram AO exposure had very similar effects on graphite fiber epoxy composites in both the EOIM-III and ORMatE-III experiments, and in neither case did bromine intercalation of the fibers substantially influence that degradation.
Intercalated graphite↗
Southern Hemisphere In Situ Observations of OH, HO2, CIO and BrO from the ER-2 Aircraft for the 1994 ASHOE Mission
A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.
Anderson, James G.↗
Measurements of halogenated organic compounds near the tropical tropopause
The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.
Schauffler, S. M.↗
Durability of Intercalated Graphite Epoxy Composites in Low Earth Orbit
The electrical conductivity of graphite epoxy composites can be substantially increased by intercalating (inserting guest atoms or molecules between the graphene planes) the graphite fibers before composite formation. The resulting high strength, low density, electrically conducting composites have been proposed for EMI shielding in spacecraft. Questions have been raised, however, about their durability in the space environment, especially with respect to outgassing of the intercalates, which are corrosive species such as bromine. To answer those concerns, six samples of bromine intercalated graphite epoxy composites were included in the third Evaluation of Oxygen Interaction with Materials (EOIM-3) experiment flown on the Space Shuttle Discovery (STS-46). Changes in electrical conductivity, optical reflectance, surface texture, and mass loss for SiO2 protected and unprotected samples were measured after being exposed to the LEO environment for 42 hours. SiO2 protected samples showed no degradation, verifying conventional protection strategies are applicable to bromine intercalated composites. The unprotected samples showed that bromine intercalation does not alter the degradation of graphite-epoxy composites. No bromine was detected to have been released by the fibers allaying fears that outgassing could be disruptive to the sensitive electronics the EMI shield is meant to protect.
Gaier, James R.↗
Measurements of Halogenated Organic Compounds near the Tropical Tropopause
The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.
Schauffler, S. M.↗
Resistivity of Carbon-Carbon Composites Halved
Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the fibers in the samples were still intercalated after composite fabrication, they were subjected to X-ray diffraction. The composites containing intercalated graphite fibers showed much higher background scatter than that of pristine fibers, indicating the presence of bromine in the samples. More importantly, faint features indicative of intercalation were visible in the diffraction pattern, showing that the fibers were still intercalated.
Gaier, James R.↗
High-Temperature Intercalated Graphite Fiber Conductors Fabricated
Composites of intercalated graphite fibers show promise to significantly reduce the weight of electromagnetic interference shielding in spacecraft and aircraft. Bromine intercalated pitch-based fibers have been among the most heavily studied systems because of their attractive electrical and thermal conductivities and their stability over a wide range of environmental conditions. Previous studies found that the resistivity of bromineintercalated graphite fibers began to increase when the fibers were exposed to temperatures in excess of about 200 C in air for long periods of time. If the temperature was as high as 450 C, the resistivity increased dramatically within a few hours. It remained unclear, however, whether the increase was due to deintercalation of the bromine or to air oxidation of the fibers. Studies were initially directed toward determining the temperature at which bromine would deintercalate from the fibers, and perhaps become a hazard to both personnel and equipment. So the mass of bromine-intercalated graphite fibers was carefully monitored as it was heated in an inert atmosphere, since the fibers are known to oxidize at a lower temperature than they deintercalate. What was found was that the fibers, which are about 18-wt% bromine, did not lose any appreciable mass even at temperatures approaching 1000 C. X-ray diffraction studies showed that there were also no changes in the overall structure of the compound. Resistivity measurements indicated that there is some slight degradation in the electronic structure, in that the resistivity increased by a few percent. Overall, the results show that these materials may be suitable for applications at temperatures at least this high, provided oxygen is excluded. This may enable their use in carbon-ceramic, and perhaps even carbon-carbon composites.
Gaier, James R.↗
Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere
Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.
Wang, Siyuan↗
BrO from the flash photolysis of Br2-N2O and Br2-NO2 mixtures
Bromine monoxide formation by atomic oxygen- bromine reaction in flash photolysis of bromine- nitrous oxide and bromine-nitrogen dioxide mixtures
Sturm, J. E.↗
Flame retardant treatments of PBI fabric.
Fabrics knitted or woven from polybenzimidazole (PBI) fibers were treated to reduce flammability in oxygen atmospheres, particularly that of 5 psia oxygen. Bromination to approximately 15% weight gain of such fabrics led to markedly lower burning rates; samples brominated to over 80% weight gain were self-extinguishing in 5 psia oxygen. The loss in tensile strength of fabrics due to bromination was negligible although shrinkage was observed. Free fibers showed negligible losses on bromination. Treatment of PBI fabric with organophosphorus compounds also achieved self-extinguishing character in 5 psia oxygen but the enhanced flameproofing was largely lost on leaching. Reaction with POCl3 in pyridine led to a permanent reduction in flammability.
Temin, S. C.↗
Graphite intercalation compound with iodine as the major intercalant
Halogenated CBr(sub x)I(sub y) (1 less than y/x less than 10) was made by exposing graphite materials with interplanar spacing in the 3.35 to 3.41 A range to either pure Br2 or an I2-Br2 mixture, and then to iodine vapor containing a small amount of Br2. The electrical resistivity of this product is from 3 to 6.5 times the pristine value. The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine to bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to fluorine attack during subsequent fluorination to fabricate graphite fluoride fibers.
Hung, Ching-Cheh↗
Graphite intercalation compound with iodine as the major intercalate
Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.
Hung, Ching-Cheh↗