Rethinking reactive halogen budgets in the midlatitude lower stratosphere

Current stratospheric models have difficulties in fully explaining the observed midlatitude ozone depletion in the lowermost stratosphere, particularly near the tropopause. Such models assume that only long-lived source gases provide significant contributions to the stratospheric halogen budget, while all the short-lived compounds are removed in the troposphere, the products being rained out. Here we show this assumption to be flawed. Using bromine species as an example, we show that in the lowermost stratosphere, where the observed midlatitude ozone trend maximizes, bromoform (CHBr3) alone likely contributes more inorganic bromine than all the conventional long-lived sources (halons and methyl bromide) combined. Copyright 1999 by the American Geophysical Union

Who Are You Going to Believe?

Although most of the time people tell the truth, people do lie. On a bad day, those working in the justice system get lied to all day long. Some days the lies are harmless, even unnecessary, and they amuse and entertain. Some of the lies are a product of self-deception: “I can quit doing drugs any time I want.” Some statements are not lies but honest mistakes: “I’m sure that is the guy who robbed me.” But on other days the lies are despicable and dangerous, and they must be exposed. The question is: Can we tell the difference between the truth and the lie? Many of us would like to believe we can rely on our professional and personal instincts to guide us, or perhaps even on some professional training we have received. Often we rely on a process we cannot precisely describe, but one in which we have confidence nonetheless. We just know. Or do we? There have been over 300 post-conviction DNA exonerations in the United States. These cases are dramatic proof that the ability of judges to determine the truth remains suspect. Eighteen people had been sentenced to death before DNA proved their innocence and led to their release. The average sentence served by DNA exonerees before their release is about 13 years.1 Exonerations have been won in 35 states and Washington, D.C. And in every case in which DNA led to exoneration, the courts were wrong in determining who was lying. The cost of that mistake could have killed someone and is a stark reminder of just how weak we are in determining who is lying

Convective transport of very short lived bromocarbons to the stratosphere

We use the NASA Goddard Earth Observing System (GEOS) Chemistry Climate Model (GEOSCCM) to quantify the contribution of the two most important brominated very short lived substances (VSLSs), bromoform (CHBr₃) and dibromomethane (CH₂Br₂), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLSs from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the tropical western Pacific, 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 active convective lofting regions mentioned above. Of the total ~8 ppt VSLS bromine that enters the base of the TTL at ~150 hPa, half is in the form of organic source gases and half in the form of inorganic product gases. Only a small portion (<10%) of the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On average, globally, 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 (strongest) and minimum (weakest) convection conditions can introduce a ~2.6 pptv uncertainty in the contribution of VSLSs to inorganic bromine in the stratosphere (Br_y^VSLS). Contrary to conventional wisdom, the minimum convection condition leads to a larger Br_y^VSLS as the reduced scavenging in soluble product gases, and thus a significant increase in product gas injection (2–3 ppt), greatly exceeds the relatively minor decrease in source gas injection (a few 10ths ppt)

When Will the Antarctic Ozone Hole Recover?

The Antarctic ozone hole demonstrates large-scale, man-made affects on our atmosphere. Surface observations now show that human produced ozone depleting substances (ODSs) are declining. The ozone hole should soon start to diminish because of this decline. Herein we demonstrate an ozone hole parametric model. This model is based upon: 1) a new algorithm for estimating C1 and Br levels over Antarctica and 2) late-spring Antarctic stratospheric temperatures. This parametric model explains 95% of the ozone hole area s variance. We use future ODS levels to predict ozone hole recovery. Full recovery to 1980 levels will occur in approximately 2068. The ozone hole area will very slowly decline over the next 2 decades. Detection of a statistically significant decrease of area will not occur until approximately 2024. We further show that nominal Antarctic stratospheric greenhouse gas forced temperature change should have a small impact on the ozone hole

Chlorine budget and partitioning during the Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE)

The amount of chlorine in the stratosphere has a direct influence on the magnitude of chlorine-catalyzed ozone loss. A comprehensive suite of organic source gases of chlorine in the stratosphere was measured during the NASA Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE) campaign in the arctic winter of 2000. Measurements included chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halon 1211, solvents, methyl chloride, N2O, and CH4. Inorganic chlorine contributions from each compound were calculated using the organic chlorine measurements, mean age of air, tropospheric trends, and a method to account for mixing in the stratosphere. Total organic chlorine measured at tropospheric levels of N2O was on the order of 3500 ppt. Total calculated inorganic chlorine at a N2O mixing ratio of 50 ppb (corresponding to a mean age of 5.5 years) was on the order of 3400 ppt. CFCs were the largest contributors to total organic chlorine (55-70%) over the measured N2O range (50-315 ppb), followed by CH3Cl (15%), solvents (5-20%), and HCFCs (5-25%). CH3Cl contribution was consistently about 15% across the organic chlorine range. Contributions to total calculated inorganic chlorine at 50 ppb N2O were 58% from CFCs, 24% from solvents, 16% from CH3Cl, and 2% from HCFCs. Updates to fractional chlorine release values for each compound relative to CFC 11 were calculated from the SOLVE measurements. An average value of 0.58 was calculated for the fractional chlorine release of CFC 11 over the 3-4 year mean age range, which was lower than the previous value of 0.80. The fractional chlorine release values for HCFCs 141b and 142b relative to CFC 11 were significantly lower than previous calculations

Estimating the climate significance of halogen-driven ozone loss in the tropical marine troposphere

We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m&lt;sup&gt;−2&lt;/sup&gt; to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m&lt;sup&gt;−2&lt;/sup&gt; contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP-3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ∼10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in the springtime troposphere of the North Pacific is responsible for this increased O3. This change is evidenced in the eastern North Pacific ITCT 2K2 study region by (1) larger increases in the minimum observed ozone levels compared to more modest increases in the maximum levels, (2) increased peroxyacetyl nitrate (PAN) levels that parallel trends in NOx, emissions, and (3) decreased efficiency of photochemical O3 destruction, i.e., less negative O3 photochemical tendency (or net rate of O3 photochemical production; P(O3)). This change photochemical environment is hypothesized to be due to anthropogenic emissions from Asia, which are believed to have substantially increased over the two decades preceding the study. We propose that their influence has changed the springtime Pacific tropospheric photochemistry from predominately ozone destroying to more nearly ozone producing. However, chemical transport model calculations indicate the possible influence of a confounding factor; unusual transport of tropical air to the western North Pacific during one early field study may have played a role in this apparent change in the photochemistry. Copyright 2004 by the American Geophysical Union