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97 records · Page 6

Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1-8 nmol/mol (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4 %. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

bromine↗

Volcanic Eruptions and Climate

Volcanic eruptions represent some of the most climatically important and societally disruptive short-term events in human history. Large eruptions inject ash, dust, sulfurous gases (e.g. SO2, H2S), halogens (e.g. Hcl and Hbr), and water vapor into the Earth's atmosphere. Sulfurous emissions principally interact with the climate by converting into sulfate aerosols that reduce incoming solar radiation, warming the stratosphere and altering ozone creation, reducing global mean surface temperature, and suppressing the hydrological cycle. In this issue, we focus on the history, processes, and consequences of these large eruptions that inject enough material into the stratosphere to significantly affect the climate system. In terms of the changes wrought on the energy balance of the Earth System, these transient events can temporarily have a radiative forcing magnitude larger than the range of solar, greenhouse gas, and land use variability over the last millennium. In simulations as well as modern and paleoclimate observations, volcanic eruptions cause large inter-annual to decadal-scale changes in climate. Active debates persist concerning their role in longer-term (multi-decadal to centennial) modification of the Earth System, however.

Volcanoes↗

Hydrogen Embrittlement

Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of hydrogen embrittlement. The effects of hydrogen gas on mechanical properties such as tensile strength, ductility, fracture, low and high cycle fatigue, crack growth rate, and creep rupture are analyzed with respect to the general trends established from the HEE index values. It is observed that the severity of HE effects is also influenced by environmental factors such as pressure, temperature, and hydrogen gas purity. The severity of HE effects is also influenced by material factors such as surface finish, heat treatment, and product forms, compositions, grain direction, and crystal orientations.

Jonathan A. Lee↗

Airborne Measurements of BrO and the Sum of HOBr and Br2 over the Tropical West Pacific from 1 to 15 Km During the CONvective TRansport of Active Species in the Tropics (CONTRAST) Experiment

A chemical ionization mass spectrometer was used to measure BrO and HOBr + Br2 over the Tropical West Pacific Ocean within the altitude range of 1 to 15 km, during the CONvective TRansport of Active Species in the Tropics (CONTRAST) campaign in 2014. Isolated episodes of elevated BrO (up to 6.6 pptv) and/or HOBr + Br2 (up to 7.3 pptv) were observed in the tropical free troposphere (TFT) and were associated with biomass burning. However, most of the time we did not observe significant BrO or HOBr + Br2 in the TFT and the tropical tropopause layer (TTL) above our limits of detection (LOD). The 1 min average LOD for BrO ranged from 0.6 to 1.6 pptv and for HOBr + Br2 ranged from 1.3 to 3.5 pptv. During one flight, BrO observations from the TTL to the extratropical lowermost stratosphere were used to infer a profile of inorganic bromine (Br(sub y)). Based on this profile, we estimated the product gas injection of bromine species into the stratosphere to be 2 pptv. Analysis of Br(sub y) partitioning further indicates that BrO levels are likely very low in the TFT environment and that future studies should target the measurement of HBr or atomic Br.

Isolated episodes of elevated BrO↗

BrO and Inferred Bry Profiles over the Western Pacific: Relevance of Inorganic Bromine Sources and a Bry Minimum in the Aged Tropical Tropopause Layer

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Br(sub y)) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January-February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry ). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6 x 10(exp 13) molec cm(exp -2), compared to model predictions of 0.9 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBr(sub y) but no SSA source), 0.4 x 10(exp 13) molec cm(exp -2) in CAM-Chem (CBr(sub y) and SSA), and 2.1 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBry and SSA). Neither global model fully captures the Cshape of the Br(sun y) profile. A local Br(sub y) maximum of 3.6 ppt (2.9-4.4 ppt; 95% confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Br(sub y) decreases from the convective TTL to the aged TTL. Analysis of gas-phase Br(sub y) against multiple tracers (CFC-11, H2O/O3 ratio, and potential temperature) reveals a Br(sub y) minimum of 2.7 ppt (2.3-3.1 ppt; 95% CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 +/- 0.6 ppt of inorganic Br(sub y) (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6-7.0 ppt; 95% CI) in the stratospheric "middleworld" and 6.9 ppt (6.5-7.3 ppt; 95% CI) in the stratospheric "overworld". The local Br(sub y) minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Br(sub y) species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Br(sub y) ) are needed to explain the gas-phase Br(sub y) budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere-Lower Stratosphere aerosols. The total Br(sub y) budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Br(sub y) species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Br(sub y) in the upper FT, (2) test Br(sub y) partitioning, and possibly explain the gas-phase Br(sub y) minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Br(sub y) to the lower stratosphere.

Atmospheric Chemistry; bromine; troposphere; CONTR↗

CA Risk Assessment Approaches

Current single-Pc approach work well when subtended by appropriate hypothesis-testing framework. Reframing construct in terms of miss distance distribution would confer certain advantages such as reducing to same import as Pc, but still convey some additional information. Methods to incorporate known uncertainties in covariances and HBR should be pursued that can also be framed in terms of miss distance distribution. We present Plausibilistic II and Possibilistic constructs, to determine their adequacy and viable recommendation.

Conjunction↗

Decision Aid for Conjunction Risk Mitigation by Differential Drag

In the previous five years, the rate of conjunctions that the NASA Conjunction Assessment Risk Analysis (CARA) team processed and analyzed has more than tripled. (NASA CARA, 2024) New missions in the early development phases are now required to plan for dealing with conjunctions under the present space environment, and also projecting forward into a future likely with even further increased utilization of the space environment. Some missions are investigating the possibility of using differential drag to remediate conjunctions without expending limited fuel or for missions without propulsive capabilities. The NASA CARA team studied the historical record of conjunctions to evaluate the circumstances under which differential drag may be successfully applied and have developed a series of tables to use as a decision aid for missions considering differential drag. Currently, if a CARA-protected mission with maneuvering capabilities is predicted to have a conjunction with probability of collision (Pc) greater than 7E-5 (the default value of the ‘yellow threshold’, which may have some other value agreed by CARA and the mission during the Orbital Collison Avoidance Planning (OCAP) process), CARA will use its Maneuver Trade Space (MTS) tool to evaluate and recommend options for the timing and magnitude of a risk mitigation maneuver (RMM), based on the mission’s capabilities. If the conjunction’s Pc is greater than 1E-4, the ‘red threshold’, then an RMM must be executed per NASA Procedural Requirements (NPR) 8079.1 (NASA, 2023), although missions may execute an RMM even if the Pc is lower. The magnitude of the maneuver is typically a few cm/s, and CARA estimates how many will be required for the mission’s nominal lifetime – typically a few per year – during the OCAP process, to inform the mission’s delta-V requirement. For traditional satellites, this is usually smaller than other requirements for orbit insertion, maintenance, and disposal, but for CubeSats or other small satellite missions, a propulsion system may not provide much more than a few cm/s of delta-V or may not fit at all within the available budget of money, time, size, weight, and/or power (SWaP). Conversely, CubeSats often have deployable solar panels, which offer the capacity to have much higher areas facing some directions than others. Such a mission can instead use ‘differential drag’ to remediate a conjunction -- in other words, change its drag area (usually increasing) to deviate from the predicted collision course. This is how Planet’s Dove spacecraft maintain their formations and remediate conjunction risks without having on-board propulsion (Foster, et al., 2017) (Griffith, et al., 2021). CARA has been developing improvements to MTS to support differential-drag for NASA's missions -- where it is effective. CARA records all conjunctions of their protected payloads, with historical records starting in 2005 (with significant conjunction events starting to occur on or after 2013). From this record, approximately 7,300 had a Pc greater than 1E-4 at 3 days prior to the time of closest approach, the time analyzed for differential drag efficacy. Of those, approximately 4,300 had fully-defined covariance matrices stored for both the primary and secondary objects; this set of conjunctions is the basis for the analysis of this work. CARA’s MTS tool was used to propagate the primary satellite forward from that decision point with varying degrees of increase to ballistic coefficient (BC). Because these conjunctions came from multiple missions, the nondimensional ‘delta-BC’ factor was used to quantify and normalize the increase in ballistic coefficient, defined as follows: Delta-BC = BC_new / BC_old - 1 Positive delta-BC factors represent an increase in drag compared to the nominal attitude, while negative delta-BC factors (to a minimum of -1) represent a decrease in drag. At the conclusion of the differential-drag ‘maneuver’, the Pc was recalculated to evaluate whether or not the conjunction was mitigated (Pc < 3E-6). These results were then binned and sorted along several axes, including altitude, amount of delta-BC, and (pre-maneuver) rate of energy dissipation (EDR), to identify underlying patterns. The altitude plot is shown in Figure 1. To validate this analysis, we consulted the record of a NASA mission which uses differential drag to maintain its orbit and remediate conjunction risk. CARA’s empirical record of the mission’s orbit history suggests it achieves a delta-BC of 2.2. Of the twenty-one RMM plans that were submitted by this mission, eighteen were matched with conjunctions in the historical record; of those, twelve were successfully remediated (final measured Pc < 3E-6), and six were not. This is consistent with the expected efficacy for missions orbiting at that altitude. We are presently simulating this mission’s RMMs with MTS; this work is ongoing, but so far, the MTS results are qualitatively in agreement with the empirical results -- correctly predicting that a maneuver would or would not remediate a conjunction, if not exactly matching the final post-remediation Pc value. We found that differential drag was most successful for satellites with perigees below 560 km, and which could adopt an average delta-BC of 2 or greater (that is, increasing their ballistic coefficient by a factor of 3). However, this is a difficult threshold for a mission to clear; very few spacecraft are capable of adopting a high-drag configuration for 72 hours continuously. Planet’s Dove spacecraft use differential drag to remediate conjunctions (Griffith, et al., 2021), and they have a maximum delta-BC factor of 9, but in practice (with mission and charging constraints) they achieve a time-averaged delta-BC that is closer to 2 (Foster, et al., 2017). A mission’s differential drag utility strongly depends on the operational constraints that has the capacity to limit the time-averaged delta-BC. A mission with a high maximum delta-BC of 5 or more can have an effective delta-BC of less than 1 due to operational constraints such as instrument and solar panel pointing, especially if this constraint results in holding an intermediate drag value for most of its orbit. CARA has developed tables that can be used as decision aids to advise missions-in-development about the best way to utilize their differential drag capabilities. For missions below 560 km with the operational flexibility to devote multiple days to holding a high-drag configuration (or a sufficiently high drag ratio to compensate for limitations on that time), they are -- more likely than not -- able to successfully remediate high-risk conjunctions. Conversely, missions that do not meet these exacting criteria -- most missions -- can instead be advised to use on-board propulsion systems to perform RMMs, or to turn their minimum-area face towards the approach vector, thereby reducing Pc at the moment of conjunction due to the decreased Hard-Body Radius (HBR), that is a strongly correlated variable in the Pc calculations. (NASA, 2023)

conjunction assessment↗