Recent Northern Hemisphere stratospheric HCl increase due to atmospheric circulation changes.

The abundance of chlorine in the Earth's atmosphere increased considerably during the 1970s to 1990s, following large emissions of anthropogenic long-lived chlorine-containing source gases, notably the chlorofluorocarbons. The chemical inertness of chlorofluorocarbons allows their transport and mixing throughout the troposphere on a global scale, before they reach the stratosphere where they release chlorine atoms that cause ozone depletion. The large ozone loss over Antarctica was the key observation that stimulated the definition and signing in 1987 of the Montreal Protocol, an international treaty establishing a schedule to reduce the production of the major chlorine- and bromine-containing halocarbons. Owing to its implementation, the near-surface total chlorine concentration showed a maximum in 1993, followed by a decrease of half a per cent to one per cent per year, in line with expectations. Remote-sensing data have revealed a peak in stratospheric chlorine after 1996, then a decrease of close to one per cent per year, in agreement with the surface observations of the chlorine source gases and model calculations. Here we present ground-based and satellite data that show a recent and significant increase, at the 2σ level, in hydrogen chloride (HCl), the main stratospheric chlorine reservoir, starting around 2007 in the lower stratosphere of the Northern Hemisphere, in contrast with the ongoing monotonic decrease of near-surface source gases. Using model simulations, we attribute this trend anomaly to a slowdown in the Northern Hemisphere atmospheric circulation, occurring over several consecutive years, transporting more aged air to the lower stratosphere, and characterized by a larger relative conversion of source gases to HCl. This short-term dynamical variability will also affect other stratospheric tracers and needs to be accounted for when studying the evolution of the stratospheric ozone layer.

Toward High Precision XCO2 Retrievals From TanSat Observations: Retrieval Improvement and Validation Against TCCON Measurements.

TanSat is the 1st Chinese carbon dioxide (CO2) measurement satellite, launched in 2016. In this study, the University of Leicester Full Physics (UoL-FP) algorithm is implemented for TanSat nadir mode XCO2 retrievals. We develop a spectrum correction method to reduce the retrieval errors by the online fitting of an 8th order Fourier series. The spectrum-correction model and its a priori parameters are developed by analyzing the solar calibration measurement. This correction provides a significant improvement to the O2 A band retrieval. Accordingly, we extend the previous TanSat single CO2 weak band retrieval to a combined O2 A and CO2 weak band retrieval. A Genetic Algorithm (GA) has been applied to determine the threshold values of post-screening filters. In total, 18.3% of the retrieved data is identified as high quality compared to the original measurements. The same quality control parameters have been used in a footprint independent multiple linear regression bias correction due to the strong correlation with the XCO2 retrieval error. Twenty sites of the Total Column Carbon Observing Network (TCCON) have been selected to validate our new approach for the TanSat XCO2 retrieval. We show that our new approach produces a significant improvement on the XCO2 retrieval accuracy and precision when compared to TCCON with an average bias and RMSE of -0.08 ppm and 1.47 ppm, respectively. The methods used in this study can help to improve the XCO2 retrieval from TanSat and subsequently the Level-2 data production, and hence will be applied in the TanSat operational XCO2 processing.

Tropospheric trace gases at Bremen measured with FTIR spectrometry.

The total column densities of acetylene (C(2)H(2)), carbon monoxide (CO), hydrogen cyanide (HCN) and ethane (C(2)H(6)) measured in Bremen (Germany, 53.107 degrees N, 8.854 degrees E) were compared with data from Mace Head/Ireland (MHD) and GEOS-Chem model simulations. The data were obtained between August 2002 and October 2006 with the ground based high resolution Fourier Transform Infra-Red (FTIR) Spectrometry, using the sun as the light source. The analysis showed good agreements between all the three data sets for the seasonal cycle of CO. Enhancements in summer 2003 and summer 2004 due to influence of biomass burning were identified in all three data sets. The high correlations between C(2)H(6) and C(2)H(2), C(2)H(2) and CO, and for C(2)H(6) and CO support the similarities in their sources and sinks. The results suggest that the background air in Bremen is mainly influenced by long-ranged transport of biomass burning products. Local pollution plays a minor role for the measurements performed in Bremen.

Importance of secondary sources in the atmospheric budgets of formic and acetic acids.

We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ∼1200 and ∼1400Gmolyr-1, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic and acetic acids well but generally underestimates their concentration, particularly in the Northern midlatitudes. We infer that the source of both carboxylic acids may be up to 50% greater than our estimate and report evidence for a long-lived missing secondary source of carboxylic acids that may be associated with the aging of organic aerosols. Vertical profiles of formic acid in the upper troposphere support a negative temperature dependence of the reaction between formic acid and the hydroxyl radical as suggested by several theoretical studies.

Solar absorption measurements of stratospheric OH in the UV with a Fourier-transform spectrometer.

We performed solar absorption measurements of OH in the UV using a Fourier-transform spectrometer (FTS). The experiments were carried out in the high Arctic at Ny- Alesund (79 degrees N, 12 degrees E) during the summer of 1996. We accomplished the analysis in two ways: (1) by studying single solar-absorption spectra recorded in the middle of the solar disk and (2) by utilizing the Doppler shift of two spectra, recorded on the east and west sides of the solar disk. The results of both analysis methods agree and give total columns of approximately 6 x 1013 molecules cm-2 for solar zenith angles of 60 degrees . To find out the main noise contribution in the spectra, we compared the measured and calculated signal-to-noise ratios (SNR 's). During clear-sky conditions the photon noise determines the total SNR. However, because a FTS is extremely sensitive to source fluctuations, conditions that were already slightly cloudy increased the scintillation noise, preventing OH analysis. The noise contribution caused by the instrumental sampling process itself was found to be negligible; even through two sampling positions had to be interpolated between the laser zero crossings.

Enhanced upper tropical tropospheric COS: impact on the stratospheric aerosol layer.

Carbonyl sulfide (COS) is considered to be a major source of the stratospheric sulfate aerosol during periods of volcanic quiescence. We measured COS at the tropical tropopause and find mixing ratios to be 20 to 50% larger than are assumed in models. The enhanced COS levels are correlated with high concentrations of biomass-burning pollutants like carbon monoxide (CO) and hydrogen cyanide (HCN). The analysis of backward trajectories and global maps of fire statistics suggest that biomass-burning emissions transported upward by deep convection are the source of the enhanced COS in the upper tropical troposphere.