Increasing concentrations of dichloromethane, CH2Cl2, inferred from CARIBIC air samples collected 1998–2012

Atmospheric concentrations of dichloromethane, CH2Cl2, a regulated toxic air pollutant and minor contributor to stratospheric ozone depletion, were reported to have peaked around 1990 and to be declining in the early part of the 21st century. Recent observations suggest this trend has reversed and that CH2Cl2 is once again increasing in the atmosphere. Despite the importance of ongoing monitoring and reporting of atmospheric CH2Cl2, no time series has been discussed in detail since 2006. The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) has analysed the halocarbon content of whole-air samples collected at altitudes of between ~10–12 km via a custom-built container installed on commercial passenger aircraft since 1998, providing a long-term record of CH2Cl2 observations. In this paper we present this unique CH2Cl2 time series, discussing key flight routes which have been used at various times over the past 15 years. Between 1998 and 2012 increases were seen in all northern hemispheric regions and at different altitudes, ranging from ~7–10 ppt in background air to ~13–15 ppt in regions with stronger emissions (equating to a 38–69% increase). Of particular interest is the rising importance of India as a source of atmospheric CH2Cl2: based on CARIBIC data we provide regional emission estimates for the Indian subcontinent and show that regional emissions have increased from 3–14 Gg yr^-1 (1998–2000) to 16–25 Gg yr^-1 (2008). Potential causes of the increasing atmospheric burden of CH2Cl2 are discussed. One possible source is the increased use of CH2Cl2 as a feedstock for the production of HFC-32, a chemical used predominantly as a replacement for ozone-depleting substances in a variety of applications including air conditioners and refrigeration

Trend and Multi‐Frequency Analysis Through Empirical Mode Decomposition: An Application to a 20‐Year Record of Atmospheric Carbonyl Sulfide Measurements

The Empirical Mode Decomposition (EMD) is a fully non-parametric analysis of frequency modes and trends in a given series that is based on the data alone. We have devised an improved strategy based on a series of best practices to use EMD successfully in the analysis of the monthly time series of carbonyl sulfide (OCS) atmospheric mole fractions measured at NOAA network stations (2000–2020). Long-term trends and intra- and inter-annual variability has been assessed. After a phase of generally increasing mole fractions up to 2015, with a temporary decline around 2009, we found that the OCS atmospheric mole fraction subsequently decreased at all stations, reflecting a recent imbalance in its total sources and losses. Our analysis has revealed a characteristic time scale for variation of 8–10 years. The variance associated with this long-term behavior ranges from urn:x-wiley:2169897X:media:jgrd58461:jgrd58461-math-000115% to 40% of the total strength of the signal, depending on location. Apart from this complex long-term behavior, the OCS time series show a strong annual cycle, which primarily results from the well-known OCS uptake by vegetation. In addition, we have also found one more frequency of minor variance intensity in the measured mole fraction time-history, which corresponds to periods in the range of 2–3 years. This inter-annual variability of OCS may be linked to the Quasi-Biennial Oscillation

Characterization of Aura TES carbonyl sulfide retrievals over ocean

We present a description of the NASA Aura Tropospheric Emission Spectrometer (TES) carbonyl sulfide (OCS) retrieval algorithm for oceanic observations, along with evaluation of the biases and uncertainties using aircraft profiles from the HIPPO (HIAPER Pole-to-Pole Observations) campaign and data from the NOAA Mauna Loa site. In general, the OCS retrievals (1) have less than 1.0 degree of freedom for signals (DOFs), (2) are sensitive in the mid-troposphere with a peak sensitivity typically between 300 and 500 hPa, (3) but have much smaller systematic errors from temperature, CO₂ and H₂O calibrations relative to random errors from measurement noise. We estimate the monthly means from TES measurements averaged over multiple years so that random errors are reduced and useful information about OCS seasonal and latitudinal variability can be derived. With this averaging, TES OCS data are found to be consistent (within the calculated uncertainties) with NOAA ground observations and HIPPO aircraft measurements. TES OCS data also captures the seasonal and latitudinal variations observed by these in situ data

Modelling marine emissions and atmospheric distributions of halocarbons and dimethyl sulfide: the influence of prescribed water concentration vs. prescribed emissions

Marine-produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethyl sulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at the ocean surface and in the atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of very short-lived substances (VSLS). We show that differences between prescribing emissions and prescribing concentrations (−28 % for CH2Br2 to +11 % for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air–sea transfer velocity (k) parameterizations, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind spee

A new multi-gas constrained model of trace gas non-homogeneous transport in firn: evaluation and behaviour at eleven polar sites

Insoluble trace gases are trapped in polar ice at the firn-ice transition, at approximately 50 to 100 m below the surface, depending primarily on the site temperature and snow accumulation. Models of trace gas transport in polar firn are used to relate firn air and ice core records of trace gases to their atmospheric history. We propose a new model based on the following contributions. First, the firn air transport model is revised in a poromechanics framework with emphasis on the non-homogeneous properties and the treatment of gravitational settling. We then derive a nonlinear least square multi-gas optimisation scheme to calculate the effective firn diffusivity (automatic diffusivity tuning). The improvements gained by the multi-gas approach are investigated (up to ten gases for a single site are included in the optimisation process). We apply the model to four Arctic (Devon Island, NEEM, North GRIP, Summit) and seven Antarctic (DE08, Berkner Island, Siple Dome, Dronning Maud Land, South Pole, Dome C, Vostok) sites and calculate their respective depth-dependent diffusivity profiles. Among these different sites, a relationship is inferred between the snow accumulation rate and an increasing thickness of the lock-in zone defined from the isotopic composition of molecular nitrogen in firn air (denoted d15N). It is associated with a reduced diffusivity value and an increased ratio of advective to diffusive flux in deep firn, which is particularly important at high accumulation rate sites. This has implications for the understanding of d15N of N2 records in ice cores, in relation with past variations of the snow accumulation rate. As the snow accumulation rate is clearly a primary control on the thickness of the lock-in zone, our new approach that allows for the estimation of the lock-in zone width as a function of accumulation may lead to a better constraint on the age difference between the ice and entrapped gases

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

The increasing threat to stratospheric ozone from dichloromethane.

It is well established that anthropogenic chlorine-containing chemicals contribute to ozone layer depletion. The successful implementation of the Montreal Protocol has led to reductions in the atmospheric concentration of many ozone-depleting gases, such as chlorofluorocarbons. As a consequence, stratospheric chlorine levels are declining and ozone is projected to return to levels observed pre-1980 later this century. However, recent observations show the atmospheric concentration of dichloromethane-an ozone-depleting gas not controlled by the Montreal Protocol-is increasing rapidly. Using atmospheric model simulations, we show that although currently modest, the impact of dichloromethane on ozone has increased markedly in recent years and if these increases continue into the future, the return of Antarctic ozone to pre-1980 levels could be substantially delayed. Sustained growth in dichloromethane would therefore offset some of the gains achieved by the Montreal Protocol, further delaying recovery of Earth's ozone layer

Atmospheric Variability Of Methyl Chloride During the Last 300 Years From an Antarctic Ice Core and Firn Air

Measurements of methyl chloride (CH3Cl) in Antarctic polar ice and firn air are used to describe the variability of atmospheric CH3Cl during the past 300 years. Firn air results from South Pole and Siple Dome suggest that the atmospheric abundance of CH3Cl increased by about 10% in the 50 years prior to 1990. Ice core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10%, with a period of about 110 years in phase with the 20th century rise inferred from firn air. Thus, the CH3Cl increase measured in firn air may largely be a result of natural processes, which may continue to affect the atmospheric CH3Cl burden during the 21st century