scholarly journals Balloon-borne radiometer measurements of Northern Hemisphere mid-latitude stratospheric HNO<sub>3</sub> profiles spanning 12 years

2007 ◽  
Vol 7 (23) ◽  
pp. 6075-6084 ◽  
Author(s):  
M. Toohey ◽  
B. M. Quine ◽  
K. Strong ◽  
P. F. Bernath ◽  
C. D. Boone ◽  
...  

Abstract. Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. We therefore find no evidence of long-term changes in the HNO3 summer mid-latitude profile, although the uncertainty of our measurements precludes a conclusive trend analysis.

2007 ◽  
Vol 7 (4) ◽  
pp. 11561-11586 ◽  
Author(s):  
M. Toohey ◽  
B. M. Quine ◽  
K. Strong ◽  
P. F. Bernath ◽  
C. D. Boone ◽  
...  

Abstract. Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and global optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. This suggests that, to within the errors of the 1990 measurements, there has been no significant change in the HNO3 summer mid-latitude profile.


2013 ◽  
Vol 13 (9) ◽  
pp. 23491-23548 ◽  
Author(s):  
A. T. Brown ◽  
M. P. Chipperfield ◽  
S. Dhomse ◽  
C. Boone ◽  
P. F. Bernath

Abstract. We present chlorine budgets calculated between 2004 and 2009 for four latitude bands (70° N–30° N, 30° N–0° N, 0° N–30° S, and 30° S–70° S). The budgets were calculated using ACE-FTS version 3.0 retrievals of the volume mixing ratios (VMRs) of 9 chlorine-containing species: CCl4, CFC-12 (CCl2F2), CFC-11 (CCl3F), COCl2, COClF, HCFC-22 (CHF2Cl), CH3Cl, HCl and ClONO2. These data were supplemented with calculated VMRs from the SLIMCAT 3-D chemical transport model (CFC-113, CFC-114, CFC-115, H-1211, H-1301, HCFC-141b, HCFC-142b, ClO and HOCl). The total chlorine profiles are dominated by chlorofluorocarbons (CFCs) and halons up to 24 km in the tropics and 19 km in the extra-tropics. In this altitude range CFCs and halons account for 58% of the total chlorine VMR. Above this altitude HCl increasingly dominates the total chlorine profile, reaching a maximum of 95% of total chlorine at 54 km. All total chlorine profiles exhibit a positive slope with altitude, suggesting that the total chlorine VMR is now decreasing with time. This conclusion is supported by the time series of the mean stratospheric total chlorine budgets which show mean decreases in total stratospheric chlorine of 0.38 ± 0.03% per year in the Northern Hemisphere extra-tropics, 0.35 ± 0.07% per year in the Northern Hemisphere tropical stratosphere, 0.54 ± 0.16% per year in the Southern Hemisphere tropics and 0.53 ± 0.12% per year in the Southern Hemisphere extra-tropical stratosphere for 2004–2009. Globally stratospheric chlorine is decreasing by 0.46 ± 0.02% per year. Both global warming potential-weighted chlorine and ozone depletion potential-weighted chlorine are decreasing at all latitudes. These results show that the Montreal Protocol has had a significant effect in reducing emissions of both ozone-depleting substances and greenhouse gases.


2016 ◽  
Author(s):  
Mike J. Newland ◽  
Patricia Martinerie ◽  
Emmanuel Witrant ◽  
Detlev Helmig ◽  
David R. Worton ◽  
...  

Abstract. The NOX (NO and NO2) and HOX (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOX and HOX are highly variable in space and time, and so the measurements of these species are of very limited value for examining long term, large scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the formation of which is dependent on the atmospheric NO / HO2 ratio. We derive long term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 4–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOX, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increase from around 1970 to the late 1990's consistent with large changes to the [NO] / [HO2] ratio in the northern hemisphere atmosphere during this period. These could represent historic changes to NOX sources and sinks. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic.


2015 ◽  
Vol 15 (8) ◽  
pp. 4215-4224 ◽  
Author(s):  
G. E. Nedoluha ◽  
D. E. Siskind ◽  
A. Lambert ◽  
C. Boone

Abstract. While global stratospheric O3 has begun to recover, there are localized regions where O3 has decreased since 1991. Specifically, we use measurements from the Halogen Occultation Experiment (HALOE) for the period 1991–2005 and the NASA Aura Microwave Limb Sounder (MLS) for the period 2004–2013 to demonstrate a significant decrease in O3 near ~ 10 hPa in the tropics. O3 in this region is very sensitive to variations in NOy, and the observed decrease can be understood as a spatially localized, yet long-term increase in NOy. In turn, using data from MLS and from the Atmospheric Chemistry Experiment (ACE), we show that the NOy variations are caused by decreases in N2O which are likely linked to long-term variations in dynamics. To illustrate how variations in dynamics can affect N2O and O3, we show that by decreasing the upwelling in the tropics, more of the N2O can photodissociate with a concomitant increase in NOy production (via N2O + O(1D) → 2NO) at 10 hPa. Ultimately, this can cause an O3 decrease of the observed magnitude.


2012 ◽  
Vol 12 (14) ◽  
pp. 6581-6592 ◽  
Author(s):  
G. Wetzel ◽  
H. Oelhaf ◽  
O. Kirner ◽  
F. Friedl-Vallon ◽  
R. Ruhnke ◽  
...  

Abstract. The winter 2009/2010 was characterized by a strong Arctic vortex with extremely cold mid-winter temperatures in the lower stratosphere associated with an intense activation of reactive chlorine compounds (ClOx) from reservoir species. Stratospheric limb emission spectra were recorded during a flight of the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 24 January 2010 inside the Arctic vortex. Several fast limb sequences of spectra (in time steps of about 10 min) were measured from nighttime photochemical equilibrium to local noon allowing the retrieval of chlorine- and nitrogen-containing species which change rapidly their concentration around the terminator between night and day. Mixing ratios of species like ClO, NO2, and N2O5 show significant changes around sunrise, which are temporally delayed due to polar stratospheric clouds reducing the direct radiative flux from the sun. ClO variations were derived for the first time from MIPAS-B spectra. Daytime ClO values of up to 1.6 ppbv are visible in a broad chlorine activated layer below 26 km correlated with low values (below 0.1 ppbv) of the chlorine reservoir species ClONO2. Observations are compared and discussed with calculations performed with the 3-dimensional Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). Mixing ratios of the species ClO, NO2, and N2O5 are well reproduced by the model during night and noon. However, the onset of ClO production and NO2 loss around the terminator in the model is not consistent with the measurements. The MIPAS-B observations along with Tropospheric Ultraviolet-Visible (TUV) radiation model calculations suggest that polar stratospheric clouds lead to a delayed start followed by a faster increase of the photodissoziation of ClOOCl and NO2 near the morning terminator since stratospheric clouds alter the direct and the diffuse flux of solar radiation. These effects are not considered in the EMAC model simulations which assume a cloudless atmosphere.


2021 ◽  
Author(s):  
Nathaniel J. Livesey ◽  
William G. Read ◽  
Lucien Froidevaux ◽  
Alyn Lambert ◽  
Michelle L. Santee ◽  
...  

Abstract. The Microwave Limb Sounder (MLS), launched on NASA's Aura spacecraft in 2004, measures vertical profiles of the abundances of key atmospheric species from the upper troposphere to the mesosphere with daily near-global coverage. We review the first 15 years of the record of H2O and N2O measurements from the MLS 190-GHz subsystem (along with other 190-GHz information), with a focus on their long-term stability, largely based on comparisons with measurements from other sensors. These comparisons generally show signs of an increasing drift in the MLS version 4 (v4) H2O record starting around 2010. Specifically, comparisons with v4.1 measurements from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) indicate a ~2–3 %/decade drift over much of the stratosphere, increasing to as much as ~7 %/decade around 46 hPa. Larger drifts, of around 7–11 %/decade, are seen in comparisons to balloon-borne frost point hygrometer measurements in the lower stratosphere. In contrast, the MLS v4 N2O product is shown to be generally decreasing over the same period (when an increase in stratospheric N2O is expected, reflecting a secular growth in emissions), with a more pronounced drift in the lower stratosphere than that found for H2O. Detailed investigations of the behavior of the MLS 190-GHz subsystem reveal a drift in its sideband fraction (the relative sensitivity of the 190-GHz receiver to the two different parts of the microwave spectrum it observes). Our studies indicate that sideband fraction drift accounts for much of the observed changes in the MLS H2O product and some portion of the changes seen in N2O. The 190-GHz sideband fraction drift has been corrected in the new version 5 MLS algorithms, which have now been used to reprocess the entire MLS record. As a result of this correction, the MLS v5 H2O record shows no statistically significant drifts compared to ACE-FTS. However, statistically significant drifts remain between MLS v5 and frost point measurements, though they are reduced. Drifts in v5 N2O are about half the size of those in v4 but remain statistically significant. Scientists are advised to use MLS v5 data in all future studies. Quantification of inter-regional and seasonal-to-annual changes in MLS H2O and N2O will not be affected by the drift. However, caution is advised in studies using the MLS record to examine long-term (multi-year) variability and trends in either of these species, especially N2O; such studies should only be undertaken in consultation with the MLS team. Importantly, this drift does not affect any of the MLS observations made in other spectral regions such as O3, HCl, CO, ClO, or temperature.


2016 ◽  
Author(s):  
Massimo Valeri ◽  
Massimo Carlotti ◽  
Jean-Marie Flaud ◽  
Piera Raspollini ◽  
Marco Ridolfi ◽  
...  

Abstract. The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) is a Fourier Transform Spectrometer that measured mid-infrared atmospheric limb emission spectra from July 2002 to April 2012 on board the polar-orbiting satellite ENVISAT. We have used MIPAS data to study the latitudinal variations of phosgene (COCl2 or carbonyl chloride) and, for the first time, its seasonal variation in the upper troposphere lower stratosphere region (UTLS). Retrievals of phosgene were made using the 830–860 cm−1 region, corresponding to the ν5 bands of COCl2. Unfortunately in that region the ν4 band of CFC-11, much stronger than COCl2 ν5, hides the phosgene emission. In order to evaluate seasonality and latitudinal distribution of phosgene we have analysed all the measurements made by MIPAS in the days 18 and 20 of each month of 2008 with the Optimized Retrieval Model (ORM) recently upgraded with the Multi-Target Retrieval technique and with the Optimal Estimation functionality to apply external constraints to the state vector. Average seasonal profiles of phosgene show an evident latitudinal variability with the largest values observed in the tropical regions (maximum ≈ 35 parts per trillion by volume (pptv) at about 300 hPa). In the mid-latitude and polar regions, the volume mixing ratios (VMR) values do not exceed 30 pptv and the vertical distributions are less peaked. Our analysis highlights that COCl2 seasonal variability is fairly low, apart from the polar regions.


2015 ◽  
Vol 15 (1) ◽  
pp. 453-480 ◽  
Author(s):  
G. E. Nedoluha ◽  
D. E. Siskind ◽  
A. Lambert ◽  
C. Boone

Abstract. While global stratospheric O3 has begun to recover, there are localized regions where O3 has decreased since 1991. Specifically, we use measurements from the Halogen Occultation Experiment (HALOE) for the period 1991–2005 and the NASA/Aura Microwave Limb Sounder (MLS) for the period 2004–2013 to demonstrate a significant decrease in O3 near ~10 hPa in the tropics. O3 in this region is very sensitive to variations in NOy, and the observed decrease can be understood as a spatially localized, yet long term increase in NOy. In turn, using data from MLS and from the Atmospheric Chemistry Experiment (ACE), we show that the NOy variations are caused by decreases in N2O which are likely linked to long term variations in dynamics. To illustrate how variations in dynamics can affect N2O and O3, we show that by decreasing the upwelling in the tropics, more of the N2O can photodissociate with a concomitant increase in NOy production (via N2O+O(1D → 2 NO) at 10 hPa. Ultimately, this can cause an O3 decrease of the observed magnitude.


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