Stratospheric Fluorine Research Articles

Stratospheric Fluorine as a Tracer of Circulation Changes: Comparison Between Infrared Remote‐Sensing Observations and Simulations With Five Modern Reanalyses

AbstractUsing multidecadal time series of ground‐based and satellite Fourier transform infrared measurements of inorganic fluorine (i.e., total fluorine resident in stratospheric fluorine reservoirs), we investigate stratospheric circulation changes over the past 20 years. The representation of these changes in five modern reanalyses is further analyzed through chemical‐transport model (CTM) simulations. From the observations but also from all reanalyses, we show that the inorganic fluorine is accumulating less rapidly in the Southern Hemisphere than in the Northern Hemisphere during the 21st century. Comparisons with a study evaluating the age‐of‐air of these reanalyses using the same CTM allow us to link this hemispheric asymmetry to changes in the Brewer‐Dobson circulation (BDC), with the age‐of‐air of the Southern Hemisphere getting younger relative to that of the Northern Hemisphere. Large differences in simulated total columns and absolute trend values are, nevertheless, depicted between our simulations driven by the five reanalyses. Superimposed on this multidecadal change, we, furthermore, confirm a 5–7‐year variability of the BDC that was first described in a recent study analyzing long‐term time series of hydrogen chloride (HCl) and nitric acid (HNO3). It is important to stress that our results, based on observations and meteorological reanalyses, are in contrast with the projections of chemistry‐climate models in response to the coupled increase of greenhouse gases and decrease of ozone‐depleting substances, calling for further investigations and the continuation of long‐term observations.

Satellite observations of stratospheric hydrogen fluoride and comparisons with SLIMCAT calculations

Abstract. 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.

Satellite observations of stratospheric carbonyl fluoride

Abstract. The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). These molecules slowly degrade in the atmosphere, leading to the formation of HF, COF2, and COClF, which are the main fluorine-containing species in the stratosphere. Ultimately both COF2 and COClF further degrade to form HF, an almost permanent reservoir of stratospheric fluorine due to its extreme stability. Carbonyl fluoride (COF2) is the second-most abundant stratospheric "inorganic" fluorine reservoir, with main sources being the atmospheric degradation of CFC-12 (CCl2F2), HCFC-22 (CHF2Cl), and CFC-113 (CF2ClCFCl2). This work reports the first global distributions of carbonyl fluoride in the Earth's atmosphere using infrared satellite remote-sensing measurements by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), which has been recording atmospheric spectra since 2004, and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, which recorded thermal emission atmospheric spectra between 2002 and 2012. The observations reveal a high degree of seasonal and latitudinal variability over the course of a year. These have been compared with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the observations agree well with each other, although MIPAS is biased high by as much as ~30%, and compare well with SLIMCAT. Between January 2004 and September 2010 COF2 grew most rapidly at altitudes above ~25 km in the southern latitudes and at altitudes below ~25 km in the northern latitudes, whereas it declined most rapidly in the tropics. These variations are attributed to changes in stratospheric dynamics over the observation period. The overall COF2 global trend over this period is calculated as 0.85 ± 0.34 (MIPAS), 0.30 ± 0.44 (ACE), and 0.88% year−1 (SLIMCAT).

Global stratospheric fluorine inventory for 2004–2009 from Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) measurements and SLIMCAT model simulations

Abstract. Fluorine-containing species can be extremely effective atmospheric greenhouse gases. We present fluorine budgets using organic and inorganic species retrieved by the ACE-FTS satellite instrument supplemented with output from the SLIMCAT 3-D chemical transport model. The budgets are calculated between 2004 and 2009 for a number of latitude bands: 70–30° N, 30–00° N, 00° N–30° S, and 30–70° S. At lower altitudes total fluorine profiles are dominated by the contribution from CFC-12, up to an altitude of 20 km in the extra-tropics and 29 km in the tropics; above these altitudes the profiles are dominated by hydrogen fluoride (HF). Our data show that total fluorine profiles at all locations have a negative slope with altitude, providing evidence that overall fluorine emissions (measured by their F content) have been increasing with time. Total stratospheric fluorine is increasing at a similar rate in the tropics: 32.5 ± 4.9 ppt yr−1 (1.31 ± 0.20% per year) in the Northern Hemisphere (NH) and 29.8 ± 5.3 ppt yr−1 (1.21 ± 0.22% per year) in the Southern Hemisphere (SH). Extra-tropical total stratospheric fluorine is also increasing at a similar rate in both the NH and SH: 28.3 ± 2.7 ppt per year (1.12 ± 0.11% per year) in the NH and 24.3 ± 3.1 ppt per year (0.96 ± 0.12% per year) in the SH. The calculation of radiative efficiency-weighted total fluorine allows the changes in radiative forcing between 2004 and 2009 to be calculated. These results show an increase in radiative forcing of between 0.23 ± 0.11% per year and 0.45 ± 0.11% per year, due to the increase in fluorine-containing species during this time. The decreasing trends in the mixing ratios of halons and chlorofluorocarbons (CFCs), due to their prohibition under the Montreal Protocol, have suppressed an increase in total fluorine caused by increasing mixing ratios of hydrofluorocarbons (HFCs). This has reduced the impact of fluorine-containing species on global warming.

A global inventory of stratospheric fluorine in 2004 based on Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE‐FTS) measurements

Total fluorine (FTOT) in the stratosphere has been determined using Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE‐FTS) measurements of HF, COF2, COClF, CF4, CCl3F (CFC‐11), CCl2F2 (CFC‐12), CHClF2 (HCFC‐22), CCl2FCClF2 (CFC‐113), CH3CClF2 (HCFC‐142b), CH2FCF3 (HFC‐134a), and SF6. The retrieval of HFC‐134a (CH2FCF3) from spaceborne measurements had not been carried out prior to this work. Measurements of these species have been supplemented by data from models to extend the altitude range of the profiles and have also been complemented by estimates of 15 minor fluorine species. Using these data, separate fluorine budgets were determined in five latitude zones (60°–82°N, 30°–60°N, 30°S–30°N, 30°–60°S, and 60°–82°S) by averaging over the period of February 2004 to January 2005 inclusive, when possible. Stratospheric FTOT profiles in each latitude zone are nearly linear, with mean stratospheric FTOT values ranging from 2.50 to 2.59 ppbv (with a 1σ precision of 0.04–0.07 ppbv and an estimated accuracy of 0.15 ppbv) for each zone. The highest mean FTOT value occurred in the tropics, which is qualitatively consistent with increasing levels of stratospheric fluorine and the mean stratospheric circulation pattern.

Ozone Depletion Update

Stratospheric ozone depletion due to chlorofluorocarbons an d increased ultraviolet radiation penetration has long been predicted. To determine if predictions of ozone depletion are correct and, if so, the significance of this depletion. Review of the English literature regarding ozone depletion and solar ultraviolet radiation. The ozone layer is showing definite thinning. Recently, significantly increased ultraviolet radiation transmission has been detected at ground level at several metering stations. It appears that man-made aerosols (air pollution) block increased UVB transmission in urban areas. Recent satellite measurements of stratospheric fluorine levels more directly implicate chlorofluorocarbons as a major source of catalytic stratospheric chlorine, although natural sources may account for up to 40% of stratospheric chlorine. Stratospheric chlorine concentrations, and resultant increased ozone destruction, will be enhanced for at least the next 70 years. The potential for increased transmission of ultraviolet radiation will exist for the next several hundred years. While little damage due to increased ultraviolet radiation has occurred so far, the potential for long-term problems is great.

Southern hemisphere ground based measurements of carbonyl fluoride (COF2) and hydrogen fluoride (HF): Partitioning between fluoride reservoir species

We report infrared ground based total column measurements of the stratospheric fluorine reservoir gases COF2 and HF above Lauder, New Zealand (45°S, 167.8°E) obtained between April 1993 and January 1994. The average retrieved COF2 and HF total columns are 2.81(±0.56)×1014 and 9.91(±1.09)×1014 molecules/cm², respectively. The daily average COF2 and HF columns are correlated; this correlation is likely the result of dynamics. The average HF/COF2 column ratio on days with measurements of both HF and COF2 is 3.63 (±0.55). Comparison of this ratio with model calculations implies that the quantum yield for COF2 photolysis is near unity. Our measured COF2 columns are higher than all previously reported values, but inconsistencies among the earlier measurements and uncertainty in the latitudinal gradient of the COF2 column preclude an accurate determination of the long‐term COF2 trend.

Stratospheric fluorine: A comparison between theory and measurements

Profiles for key stratospheric fluorine species are presented along with HF:HCl ratio. Discrepancies between theory and observation are examined and their implications are discussed. Our results indicate that the HF:HCl ratio depends critically on OH concentration between 20‐30 km and it might provide an indirect check on the present stratospheric OH chemistry or H2O abundances which are of central importance to stratospheric chemical processes.